Laminate for printing and, printing method and printed matter using the same

ABSTRACT

A laminate for printing for coloring a resin layer by allowing a sublimable dyeing agent to permeate into the inside of the resin layer through heating, which comprises, in the order from the surface, a surface resin layer A( 1 ) having a weak affinity with the sublimable dyeing agent and allowing the dyeing agent to pass through it and a coloring resin layer B( 12 ) having strong affinity with the dyeing agent and preventing the transfer of the dyeing agent; and a printing method and a printed mater using the lamainate. The laminate for printing has, formed as an inner layer, a coloring resin layer having strong affinity with a sublimable dyeing agent and capable of preventing the transfer of the dyeing agent, which allows the prevention of the transfer of a sublimable dyeing agent having been printed.

TECHNICAL FIELD

The present invention relates to a printing laminate that is used forsublimation dyeing in which a sublimable dye is allowed to penetrate theinside of a resin by the application of heat and relates to a printingmethod and a print using the printing laminate. More specifically, thepresent invention relates to a printing laminate that prevents themigration of a sublimable dye, which occurs during the dyeing or occursover the course of time after the dyeing, and relates to a printingmethod and a print using the printing laminate.

BACKGROUND ART

Conventionally, when an image or the like is printed on a printinglaminate using a sublimable dye, the printing is conducted first onpaper using an ink containing the sublimable dye, and then the printedsurface of the paper is applied to a surface of the printing laminateand the printed surface of the paper is brought into intimate contactwith the printing laminate by means of a heat vacuum applicator, aheated roll or the like so as to conduct thermal compression forallowing the sublimable dye to penetrate the inside of the printinglaminate. As another conventional method, printing is conducted using anink containing a sublimable dye with respect to a temporary displayingsurface layer, which is provided at a surface of a printing laminate inorder to accept the ink, followed by heating so as to allow the dye todiffuse and penetrate inside the printing laminate, whereby a printedimage to be attained can be realized. During the printing, the dye thatis sublimated to have a molecular size penetrates the inside of a resin,so that an image is printed by developing colors in a colorable resinlayer. In this step, however, if the transfer temperature and thetransfer time are lower and shorter than the optimum conditions for thetransfer printing, sufficient density of the colors cannot be obtained.Alternatively, if they are in excess of the optimum conditions, problemsoccur in which the sublimable dye extends to penetrate and migrate intoa layer continuous with the colorable resin layer, such as a glue layerand an adhesive layer that are provided for the attachment to asubstrate, which impairs the sharpness of the image or makes the edge ofthe image blurred. In addition, even when the printing is conducted bysublimation dyeing under the optimum conditions, the dye graduallymigrates to the afore-mentioned layers that are continuous with thecolorable resin layer over the course of time. This means the diffusionof the dye that is to be kept within the colorable resin layer, whichcauses the problems of discoloration, the blurred edge of an image andthe like. As a conventional example, when a printing laminate ismanufactured, a colorable resin layer, a surface resin layer and thelike are laminated successively on a substrate film made of polyester,etc., so as to manufacture the printing laminate, which is proposed inJP 2002-79751 A, for example.

However, the technology of JP 2002-79751 A has the problem that, when apolyester film used is not stretched, the migration of a dye cannot beprevented. When a biaxially stretched polyester film is used, theinterlayer migration of the dye can be prevented to some extent becausethe biaxially stretched polyester film has an enhanced crystallinity andintermolecular density of the resin due to the stretching. However, sucha film also is insufficient for keeping the sharpness of an image for along time within the colorable layer, and the edge of the printed imagebecomes blurred in a short time. Furthermore, when a biaxially stretchedpolyester film is adopted as a substrate used in the course of themanufacturing process, the biaxially stretched polyester film contractsdue to the heat applied during the sublimation dyeing, which causes aproblem that wrinkles and streaks occur in the printing laminate.

In addition, in the case where the biaxially stretched polyester film isto be attached on a three-dimensionally curved surface, for example, forwrapping vehicles, it becomes difficult to attach the film on the curvedsurface because the film lacks flexibility, elongation percentage andthe like because of its stiffness. Thus, there is a demand in the marketfor developing a novel printing laminate used for sublimation dyeingthat can keep the density of colors of an image for a long time periodand can keep the sharpness of the image, is free from wrinkles andstreaks that might occur during the heating for transfer and hasexcellent suitability for the attachment on a three-dimensionally curvedsurface.

DISCLOSURE OF THE INVENTION

In order to cope with the above-stated problems, it is a first object ofthe present invention to provide a printing laminate that can preventthe migration of a sublimable dye and to provide a printing method and aprint using the printing laminate.

It is a second object of the present invention to provide a printinglaminate that has flexibility for allowing the printing laminate to beattached on a curved surface and to provide a printing method and aprint using the printing laminate.

In order to fulfill the above first object, a printing laminateaccording to the present invention, in which a sublimable dye is allowedto penetrate an inside of a resin layer by application of heat so as tocolor the resin layer, includes the following layers being laminated inthis stated order from a surface of the laminate: a surface resin layer(A) that has weak affinity with the sublimable dye and that has apermeability of the dye; and a dye migration preventive colorable resinlayer (B) that has affinity with the dye and prevents migration of thedye, or a colorable resin layer (B1) that has affinity with the dye anda dye migration preventive layer (B2) that prevents migration of thedye.

Next, in order to fulfill the above second object, a printing laminateaccording to the present invention includes a flexible resin layer (C)that has an elongation percentage larger than that of the dye migrationpreventive colorable resin layer (B), the flexible resin layer (C) beingprovided at a further lower layer than the dye migration preventivecolorable resin layer (B).

A printing method of the present invention, by which printing isconducted with respect to a printing laminate in which a sublimable dyeis allowed to penetrate an inside of a resin layer by application ofheat so as to color the resin layer, the printing laminate including, asurface resin layer (A) that has weak affinity with the sublimable dyeand that has a permeability of the dye; and a dye migration preventivecolorable resin layer (B) that has affinity with the dye and preventsmigration of the dye, which are laminated in this stated order from asurface of the laminate. The printing method includes the steps of:conducting printing with respect to a transfer paper using an inkcontaining a sublimable dye; and bringing an image formation face of thetransfer paper in contact with the surface resin layer (A), followed bya heat treatment so as to sublimate the sublimable dye, thus allowingdiffusion of the sublimable dye into the dye migration preventivecolorable layer (B) or a colorable resin layer (B1) to dye the same.

A print of the present invention, with respect to which printing isconducted using a printing laminate in which a sublimable dye is allowedto penetrate an inside of a resin layer by application of heat so as tocolor the resin layer, the printing laminate including, a surface resinlayer (A) that has weak affinity with the sublimable dye and that has apermeability of the dye; and a dye migration preventive colorable resinlayer (B) that has affinity with the dye and prevents migration of thedye, which are laminated in this stated order from a surface of thelaminate. The printing is conducted with respect to a transfer paperusing an ink containing a sublimable dye; and an image formation face ofthe transfer paper is brought in contact with the surface resin layer(A), followed by a heat treatment so as to sublimate the sublimable dye,thus allowing diffusion of the sublimable dye into the dye migrationpreventive colorable layer (B) or a colorable resin layer (B1) to dyethe same.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cross-sectional view of a printing laminate according to oneembodiment of the present invention.

FIG. 2 is a cross-sectional view of a printing laminate according toanother embodiment of the present invention.

FIG. 3 is a cross-sectional view of a printing laminate according tostill another embodiment of the present invention.

FIG. 4 is a cross-sectional view of a printing laminate according to afurther embodiment of the present invention.

FIG. 5 is a cross-sectional view of a printing laminate according to astill further embodiment of the present invention.

FIG. 6 is a cross-sectional view of a printing laminate according toanother embodiment of the present invention.

FIG. 7 is a cross-sectional view of a printing laminate according tostill another embodiment of the present invention.

FIG. 8 shows the steps for manufacturing a further embodiment of thepresent invention, wherein FIG. 8A schematically shows the cross-sectionof a portion in which a glass beads temporary zing layer is formed on apolyester film, on a surface of which transparent glass beads areembedded and a metal reflective layer is formed thereon; FIG. 8Bschematically shows the cross-section of a portion in which a primerlayer is formed on a polyester film and a supporting resin sheet isformed thereon; FIG. 8C schematically shows the cross-section of aportion in which the supporting resin sheet is brought along the surfaceof the glass beads temporary fixing layer; FIG. 8D schematically showsthe cross-section of a portion in which pressure is applied to thesupporting resin sheet toward the surface of the glass beads temporaryfixing layer; FIG. 8E schematically shows the cross-section of a portionin which the polyester film together with the glass beads temporaryfixing layer are peeled off from the surface of the supporting resinsheet; FIG. 8F schematically shows the cross-section of a portion in astate where the surface of the supporting resin sheet is covered withthe printing laminate of the present invention before thermo compressionshaping is performed using a patterned emboss roll; and FIG. 8Gschematically shows the cross-section of a portion in which the thermocompression shaping is being performed using the patterned emboss roll.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, a surface resin layer (A) that has weakaffinity with a sublimable dye and that has a permeability of the dye;and a dye migration preventive colorable resin layer (B) that hasaffinity with the dye and prevents migration of the dye are included.This lamination of the surface resin layer (A) on the dye migrationpreventive colorable resin layer (B) allows the sublimable dye to passthrough the surface resin layer (A) easily by application of heat andallows the same to penetrate the colorable resin layer (B) of theprinting laminate. In addition, the dye kept in the colorable resinlayer can be protected from ultraviolet rays, water and the like, thusenhancing the resistance to fading. Furthermore, the colorable resinlayer has a capability of preventing the migration of the dye, which canprevent the discoloration and the blurred edge of an image, resultingfrom the migration of the dye to a layer that is not to be colored.

The afore-mentioned dye migration preventive colorable resin layer (B)may be formed to include separate layers of: a colorable resin layer(B1) that has affinity with the dye; and a dye migration preventivelayer (B2) that prevents migration of the dye, which are laminated inthis order from the surface of the laminate. The provision of the dyemigration preventive layer below the colorable resin layer can preventthe discoloration and the blurred edge of an image more effectively,resulting from the migration of the dye to a lower layer that is not tobe colored.

Next, a flexible resin layer (C) may be provided to have an elongationpercentage larger than that of the dye migration preventive colorableresin layer (B) or the dye migration preventive layer (B2) at a furtherlower layer than the dye migration preventive colorable resin layer (B)or the dye migration preventive layer (B2). This configuration canprevent the generation of cracks in the dye migration preventive layereven when the printing laminate of the present invention is stretchedfor the attachment on a substrate having a three-dimensionally curvedsurface, thus avoiding the dye from migrating to other layers throughthe cracks. Thereby, flexibility can be given to the printing laminate,thus enabling the attachment of the printing laminate on athree-dimensionally curved substrate.

In the present invention, it is preferable that the dye migrationpreventive colorable resin layer (B) or the dye migration preventivelayer (B2) is made of a resin containing as a main component a vinylresin having a SP value (Solubility Parameter) of 9.0 or more. Such ause of the resin containing as a main component a vinyl resin having aSP value of 9.0 or more for the dye migration preventive layer enablesmore effective prevention of the dye migration.

Furthermore, when a biaxially stretched film is used as the dyemigration preventive colorable resin layer (B) or the dye migrationpreventive layer (B2), it is preferable that the biaxially stretchedfilm is stretched by 10% or more in a winding direction and in a widthdirection and that has a shrinkage ratio of 1.0% or less in the windingdirection of the film at the time of heating at 150° C. for 30 minutes.Such a use of a biaxially stretched film with a low shrinkage ratio forthe dye migration preventive layer can prevent wrinkles and streaks,which might occur during the sublimation dyeing.

Furthermore, it is preferable that the surface resin layer (A) is formedof a fluororesin containing a fluoroolefin copolymer that is soluble ina solvent. Such a use of the fluoroolefin copolymer that is soluble in asolvent for the surface resin layer (A) of the present invention allowsthe sublimable dye to penetrate efficiently the colorable resin layerwithin the printing laminate by application of heat, thus furtherenhancing the outdoor weathering resistance.

Furthermore, the surface resin layer (A) may be formed of a silicondenatured acrylic resin. Such a use of a silicon denatured acrylic resinfor the surface resin layer (A) of the printing laminate allows thesublimable dye to penetrate efficiently the colorable resin layer withinthe printing laminate by application of heat, thus further enhancing theoutdoor weathering resistance.

Furthermore, it is preferable that the dye migration preventivecolorable resin layer (B) or the colorable resin layer (B1) does notcontain a low molecular-weight compound of a content exceeding about 20weight %, the low molecular-weight compound having a molecular weight ofabout 1,300 or less. Such a reduction of the low molecular-weightcompound contained in the colorable resin layer can enhance the effectof preventing the migration of the dye.

Furthermore, a matting agent may be added to the surface resin layer (A)so as to decrease a 60° gloss (method 3 (60° relative-specularglossiness) specified by JIS Z 8741 (method for measuringrelative-specular glossiness)) of the surface resin layer to 70 or less.This configuration is preferable because the reflection by lightequipment such as a fluorescent lamp can be prevented.

Furthermore, it is preferable that at least one layer of the surfaceresin layer (A), the dye migration preventive colorable resin layer (B)and the colorable resin layer (B1) contains at least one type selectedfrom the group consisting of an ultraviolet absorber, a lightstabilizer, and an antioxidant in order to prevent the discoloration ofan image and enhance the durability of the resin. The ultravioletabsorber, the light stabilizer, and the antioxidant used here preferablyare a high-molecular weight type. Such a high-molecular weight typeultraviolet absorber, light stabilizer, and antioxidant can reduce: theoccurrence of phase caused by the phase separation from transparentresin such as the surface layer; deficiencies such as bleed-out; and avolatilization amount during a thermal sublimation processing, thusenabling the formation of a transparent resin that is stable for a longtime and enabling the prevention of an image from ultraviolet rays orthe like for a long time.

Furthermore, light diffusing fine particles may be added to at least onelayer of the surface resin layer (A), the dye migration preventivecolorable resin layer (B), the dye migration preventive layer (B2) andeach layer below these layers, so as to assign a light diffusingproperty to these layers. Thereby, the printing laminate can be used asa film for backlight by illuminating the printing laminate from a rearface.

Furthermore, a white pigment may be used for at least one layer of thedye migration preventive colorable resin layer (B), the colorable resinlayer (B1) and the dye migration preventive layer (B2) so as to form awhite layer. This configuration enhances a transmittance density of aprinted image.

Furthermore, a layer including high refractive glass beads may belaminated at a lower layer of the dye migration preventive colorableresin layer (B), the dye migration preventive layer (B2) or the flexibleresin layer (C) and a metal reflective layer further may be coated andformed at a lower layer of the layer including the high refractive glassbeads, so as to provide a retroreflective layer. This configuration ispreferable because retroreflection can be performed by the printinglaminate using the illumination such as a headlight of vehicles in thenighttime, thus enhancing the visibility of the print in the nighttime,which results in significant enhancement of effects for traffic safetyand advertisement.

Similarly, a layer in which high refractive glass beads are fixed and afocus resin layer may be laminated successively at lower layers of thedye migration preventive colorable resin layer (B), the dye migrationpreventive layer (B2) or the flexible resin layer (C), and a metalreflective layer further may be coated and formed at a lower layer ofthe focus resin layer, so as to provide a retroreflective layer. Thisconfiguration is preferable for the same effects as stated above.

Moreover, in a retroreflective sheet including: a plurality oftransparent beads whose lower hemispheres are each provided with a metalreflective layer; a supporting resin sheet supporting the plurality oftransparent beads; and a transparent cover film covering the pluralityof transparent beads by being disposed on a surface side of thesupporting resin sheet, a bonding portion for holding the cover film maybe provided in the supporting resin sheet, and the cover film may be theafore-mentioned printing laminate. This configuration is more preferablebecause such a printing laminate enables much brighter retroreflectionthan the afore-mentioned retroreflection.

Furthermore, the surface resin layer of the afore-mentioned printinglaminate may be coated with a coating formation composition includingfine particles made of hydrotalcites and metal oxide, the hydrotalcitesbeing represented by [M²⁺ _(1-X)M³⁺ _(X)(OH)₂]^(X+)[A^(n−)_(X/n).mH₂O]^(X−), wherein M²⁺ denotes divalent metal ions, M³⁺ denotestrivalent metal ions, A^(n−) denotes anions, 0<X≦0.33, 0≦m≦2. Thisconfiguration is preferable, because contamination substances will notbe attached thereon over a long term, thus allowing a sharp image to bedisplayed.

Furthermore, it is preferable that an antistatic treatment is applied toan adhesive layer provided on a rear face of the printing laminate or areleasing member such as a releasing film or a releasing paper appliedto the adhesive layer or a glue layer. Such an antistatic treatmentapplied to the releasing member such as a releasing film or a releasingpaper can prevent the instability of a printed image, caused byfluctuations in the discharge direction of an ink from a nozzle forprinting, which results from the static electricity generated when thesheet is wound off or the static electricity generated by the frictionbetween the printing laminate and a printer during the printing by anink jet printer. Thus, a precise image can be formed.

Moreover, the printing laminate may be provided with at least one layerof peelable temporary displaying layer for enabling printing anddisplaying on the surface resin layer (A), and a face of the temporarydisplaying layer on a side that does not contact with the surface resinlayer (A) may be capable of absorbing an ink containing a sublimable dyeand may be capable of allowing the sublimable dye to sublimate byapplication of heat so as to allow diffusion and dyeing in the printinglaminate, and after heating, the temporary displaying layer may becapable of being peeled off from the surface resin layer of the printinglaminate while keeping a film state. This configuration is preferablebecause a desired image can be printed directly on the printing laminateusing a sublimable dye, and the following heat treatment can realize asharp image keeping an excellent weathering resistance easily.

According to the printing method of the present invention, the printingis conducted with respect to a transfer paper using an ink containing asublimable dye; and an image formation face of the transfer paper isbrought in contact with the surface resin layer (A), followed by a heattreatment so as to sublimate the sublimable dye, thus allowing diffusionof the sublimable dye into the dye migration preventive colorable layer(B) or a colorable resin layer (B1) to dye the same.

Furthermore, printing may be conducted with respect to at least onelayer of peelable temporary displaying layer by a well-known method suchas an ink jet printer, a heat transfer printer and a laser printer, anda resultant can be used as a laminate for temporary display. When the nolonger needed temporary displaying layer is peeled off, a substrate onwhich the printing laminate of the present invention has been attachedcan be visually recognized, which can be used as a transparentprotective film for the substrate.

Furthermore, printing may be conducted with respect to the temporarydisplaying layer using an ink containing a sublimable dye, followed by aheat treatment so as to allow the sublimable dye to sublimate. Thereby,a sharp image keeping high weathering resistance can be obtained.

Furthermore, preferably, the printing is conducted by an ink jet method,in particular, using an ink jet printer capable of full color printingwith easiness.

Furthermore, it is preferable that a temperature of the heat treatmentafter printing is within a range from 150 to 200° C. This is becausesuch a range of temperature allows the sublimation of the sublimable dyein a short time without thermal damage on a releasing film or the likeon a rear face of the printing laminate, thus making the workabilitybetter.

Moreover, the printed surface preferably is dried before the heattreatment, because the diffusion of the sublimable dye can be madeuniform during the heat treatment.

The following describes the printing laminate of the present inventionin detail, by way of embodiments.

FIG. 1 shows a configuration of a printing laminate of the presentinvention. Beneath the printing laminate may be provided with areleasing paper or a releasing film that is integrated with the printinglaminate via a glue layer or an adhesive layer. As a material that isavailable for a colorable resin layer, a synthetic resin having affinitywith a dye preferably is used for capturing the sublimated and diffuseddye with efficiency and for developing colors with high density. Morepreferably, a heat-resistant resin may be applied so as to avoid thesoftening considerably occurring at a heating temperature from about150° C. to 200° C. during the sublimation dyeing and the occurrence oftuck (sticky, so-called adhesion). In particular, a resin curable withradioactive rays preferably is used. The effective forms of theradioactive rays include electron beams, ultraviolet rays, nuclearradiation, microwave radioactive rays and heat, and substances curablewith the radioactive rays are well-known in the pertinent art.Furthermore, it is preferable, from the viewpoint of the protection ofthe dye from ultraviolet rays and the like, that an ultraviolet absorberis dispersed uniformly and included in the colorable resin layer in theamount for enabling 70% or more of ultraviolet rays to be filtered outby the colorable resin layer itself, preferably 80% or more, and morepreferably 90% or more. More specifically, available materialssatisfying such required properties include synthetic resins such asvinyl resins, acrylic resins, alkyd resins, polyester resins, urethaneresins and epoxy resins.

Low molecular-weight compounds in the resin cause the migration of theonce fixed dye gradually, which results in problems such as the blurrededge of an image. To avoid this, it is preferable to make the colorableresin layer free from the residue of the low molecular-weight compoundsand to minimize the usage of an additive such as a plasticizer. Tominimize the low molecular-weight compounds contained in the colorableresin layer is an effective way to keep a stable image. Theafore-mentioned low molecular-weight compounds are compounds with amolecular weight of about 1300 or less, whose content is about 20 weight% or less, preferably about 15 weight % or less and more preferablyabout 10 weight % or less. If the low molecular-weight compounds withmolecular weight of about 1300 or less are used in excess of about 20weight %, the printed image tends to become blurred at the edge in ashort time.

A printing laminate that is colored by a sublimation dyeing method maybe provided with a layer of a glue or an adhesive on a rear face side ofthe colorable resin layer. Then, the printing laminate may be used whilebeing attached to a substrate made of metal, wood, plastic, glass andthe like, or may be used while being sandwiched between plastics. Inthis state, however, the dye may diffuse and migrate gradually from thecolorable resin layer to the glue or the adhesive or the plasticssandwiching the laminate. As a result, problems may occur such thatbleeding occurs in the image or an edge of the image becomes blurred, orthe printed colors blend with each other so as to degrade the sharpnessof the image.

In order to cope with these problems, an effective way is to give acapability of preventing the migration of the dye to the colorable resinlayer or to provide a dye migration preventive layer that is continuouswith the colorable resin layer, the migration preventive layer being forpreventing the migration of the dye.

One example of preferable materials having the dye migration preventivecapability or used as the dye migration preventive layer is a biaxiallystretched film. In particular, a biaxially stretched film in an advancedstate of crystallization and with an increased intermolecular density ispreferable. Among others, a biaxially stretched film that is stretchedby 10% or more in the winding direction and in the width direction,respectively, is preferable, more preferably by 50% or more, muchpreferably by 100% or more and particularly preferably by 200% or more.The stretching percentage less than 10% is insufficient for preventingthe migration of a sublimable dye, and moreover there is still anotherproblem that the biaxially stretched polyester film contracts due to theheat applied for allowing a sublimable dye to penetrate inside a resinto color the resin, which causes wrinkles and streaks. In order to copewith this problem, after the biaxial stretching, annealing preferably isperformed to the film at a temperature of the glass transitiontemperature or higher, in which heat is applied so as to fix the lengthof the film or to allow the film to relax. The application of the filmwhose shrinkage ratio at the time of heating at 150° C. for 30 minutesis 1.0% or less in the winding direction of the film is preferable, morepreferably, 0.8% or less and much preferably 0.6% or less. When thebiaxially stretched polyester film whose shrinkage ratio exceeds 1.0% isused, the heat applied for allowing a sublimable dye to penetrate insidea resin to color the resin would cause deficiencies that impair theappearance, such as wrinkles and streaks, and therefore such a film isnot preferable. In the case of the biaxially stretched polyester film,the stretching allows the orientation of polymer molecules to advance,thus increasing a degree of the crystallinity and increasing thesurfaces of the polymer molecules contacting with each other in size.Conceivably, this results in an increase of the intermolecularattracting forces of the polymer, which can prevent the migration of thedye from the colorable resin layer with efficiency. However, thebiaxially stretched polyester film lacks an elongation percentagebecause of the stiffness, and therefore when the biaxially stretchedpolyester film is used as the dye migration preventive layer, it isdifficult to attach the film on a three-dimensionally curved surface.

Then, as a result of keen examination to accomplish the invention of anovel dye migration preventive layer that can keep a dye migrationpreventive capability in lieu of the biaxially stretched film, theinventors of the present invention succeeded in obtaining a dyemigration preventive layer that has an excellent dye migrationpreventive capability by forming the dye migration preventive layer witha resin containing as a main component a vinyl resin having a SP value(Solubility Parameter) of 9.0 or more. When the migration of asublimable dye is to be prevented using a vinyl resin, the vinyl resinwith a SP value of 9.0 or more preferably is used, more preferably 9.25or more and much preferably 9.50 or more. A resin containing these vinylresins as main components may be used in an uncured state, or may beused with a curable substance so that they are used as athree-dimensionally structured cross-linked polymer. This configurationis preferable because it can prevent the migration of a sublimable dye.

The SP value mentioned here is a parameter indicating the polarity of aresin. A higher SP value indicates a higher polarity of the resin.

The SP value can be measured by a method described later. Herein, the SPvalue of vinyl copolymers can be estimated by measuring a SP value of ahomopolymer of a used vinyl monomer beforehand. That is to say, the SPvalue of a copolymer can be estimated from the sum of the valuesobtained by multiplying the weight fractions of the individual vinylmonomers constituting the copolymer with the SP values of thehomopolymers.

Actual measurements of SP values of typical homopolymers are as follows:methyl methacrylate=10.6, n-butyl methacrylate=8.4, ethylmethacrylate=9.5, β-hydroxy ethyl methacrylate=11.5, n-butylacrylate=8.6 and the like.

For instance, a SP value of the copolymer including methylmethacrylate/n-butyl methacrylate/β-hydroxy ethyl methacrylate=50/40/10(weight ratio) can be calculated as(10.6×0.5)+(8.6×0.4)+(11.5×0.1)=9.89, which is closer to the value of9.92 obtained by the following actual measurement of the SP value ofthis copolymer.

A method for measuring SP values of vinyl resins is as follows:

A resin with a solid content of 0.5 g is weighed in a 100 ml Mayerflask, and 10 ml of tetrahydrofuran (THF) is added thereto so as todissolve the resin. The dissolved solution is kept at a liquidtemperature of 25° C., and hexane is dropped using a 50 ml buret whilestirring with a magnetic stirrer. Then, the dropped amount (V_(h)) isdetermined at the time when the solution generates turbidity (turbidpoint).

Next, the dropped amount (V_(d)) is determined at the turbid point whendeionized water is used instead of hexane.

From V_(h), V_(d), the SP value δ of this resin can be determined usingthe formula given by SUH, CLARKE [J.Polym.Sci.A-1,Vol.5,1671-1681(1967)] as follows:δ=[(V _(mh))^((1/2))δ_(mh)+(V _(md))^((1/2))δ_(md)]/[(V_(mh))^((1/2))+(V_(md))^((1/2))]whereV _(mh)=(V _(h) ·V _(t))/(φ_(h) ·V _(t)+φ_(t) ·V _(h)),V _(md)=(V _(d) ·V _(t))/(φ_(d) ·V _(t)+φ_(t) ·V _(d))δ_(mh)=φ_(h)·δ_(h)+φ_(t)·δ_(t)δ_(md)=φ_(d)·δ_(d)+φ_(t)·δ_(t)φ_(h), φ_(d), φ_(t); volume fraction of hexane, deionized water and THFat turbid point(φ_(h) =V _(h)/(V _(h)+10), φ_(d) =V _(d)/(V _(d)+10))δ_(h), δ_(d), δ_(t); SP values of hexane, deionized water and THFV_(h), V_(d), V_(t); molecular volume of hexane, deionized water and THF(ml/mol)

Next, vinyl monomers used for synthesizing vinyl resins include: variousaromatic series vinyl monomers such as styrene, α-methyl styrene,p-t-butyl styrene and vinyltoluene;

Various (meth)acrylates such as methyl(meth)acrylate,ethyl(meth)acrylate, n-propyl(meth)acrylate, i-propyl(meth)acrylate,n-butyl(meth)acrylate, i-butyl(meth)acrylate, t-butyl(meth)acrylate,2-ethylhexyl (meth)acrylate, lauryl(meth)acrylate,cyclohexyl(meth)acrylate, benzyl (meth)acrylate,isobornyl(meth)acrylate, dibromopropyl(meth)acrylate,tribromophenyl(meth)acrylate and alkoxyalkyl(meth)acrylate;

Diesters of unsaturated dicarboxylic acid, such as maleic acid, fumaricacid and itaconic acid, and monohydric alcohol;

Various vinyl esters such as vinyl acetate, vinyl benzoate and “VEOVA”(trade name, vinyl ester produced by Japan Epoxy Resins Co., Ltd.);

(Per)fluoro alkyl group-containing vinyl esters such as “VISKOTE 8F,8FM, 17FM, 3F or 3FM” (trade name, fluorine-containing acrylic monomerproduced by Osaka Organic Chemical Industry Ltd.), perfluoro cyclohexyl(meth)acrylate, di-perfluoro cyclohexyl fumarate and N-i-propylperfluoro octanesulfone amidoethyl(meth)acrylate, or variousfluorine-containing polymerizable compounds such as vinyl ethers,(meth)acrylates and unsaturated polycarboxylic acid esters;

Vinyl monomers that have not functional groups such as olefins, such asvinyl chloride, vinylidene chloride, vinyl fluoride, vinylidenefluoride, trifluoroethylene and chlorotrifluoropropylene;

Various amide bond containing vinyl monomers such as (meth)acrylamide,dimethyl(meth)acrylamide, N-t-butyl(meth)acrylamide,N-octyl(meth)acrylamide, diacetone acrylamide, dimethyl aminopropylacrylamide and alkoxylated N-methylolated(meth)acrylamides;

Various dialkylamino alkyl(meth)acrylates such as dimethylaminoethyl(meth)acrylate and diethylamino ethyl(meth)acrylate;

Carboxyl group-containing vinyl monomers such as (meth)acrylic acid,crotonic acid, maleic acid, fumaric acid and itaconic acid; and

Hydroxyl group containing (meth)acrylates such as2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,3-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate,3-hydroxybutyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate.

Furthermore, other copolymerizable vinyl monomers include(meth)acrylonitrile, glycidyl(meth)acrylate,(β-methyl)glycidyl(meth)acrylate, allyl glycidyl ether, vinyl ethoxysilane, α-methacryloxy propyltrimethoxy silane,trimethysiloxyethyl(meth)acrylate and the like.

The vinyl resins used in the present invention can be prepared using therespective components as raw materials including vinyl monomers by awell-known polymerization (reaction) method such as a batch type, asemi-batch type or a continuous type solution polymerization methodunder normal pressure or under pressure. In this step, variouswell-known radical generative polymerization catalysts such asazobisisobutyronitrile, benzoyl peroxide, t-butyl peroxy benzoate,t-butyl peroxy-2-ethyl hexanoate, t-butyl hydroperoxide, di-t-butylperoxide and cumene hydroperoxide can be used alone or by mixing severaltypes depending on the polymerization condition.

As solvents used for the solution polymerization, aromatic hydrocarbonssuch as toluene and xylene and solvents such as ester solvents, ketonesolvents and alcohol solvents may be selected as needed.

The following describes an example where preferable vinyl resins with SPvalues of 9.0 or more are synthesized.

REFERENCE EXAMPLE 1

1000 parts of n-butyl acetate was put in a four-necked flask equippedwith a stirrer, a thermometer, an inner gas inlet and a condenser, and atemperature was increased to 100° C. Next, a mixture including: 650parts of methyl methacrylate; 245 parts of n-butyl methacrylate; 100parts of 2-hydroxy ethyl methacrylate; 5 parts of methacrylic acid; and15 parts of t-butyl peroxy-2-ethyl hexanoate was dropped at 110° C. over4 hours, and even after the dropping, the temperature was kept at 110°C. so as to continue the reaction for 6 hours, whereby vinyl copolymer(a-1) having about a nonvolatile content of 50% was obtained. This vinylcopolymer (a-1) was dried and its SP value was measured. The measurementresult was 10.16.

REFERENCE EXAMPLES 2 TO 6

Vinyl copolymers (a-2) to (a-6) were obtained in a similar manner toReference Example 1 except that the ratio of vinyl monomers was changedas in Table 1. Furthermore, they were dried and their SP values weremeasured. The measurement results are shown in Table 1.

TABLE 1 Vinyl monomers a-2 a-3 a-4 a-5 a-6 styrene 100 200 200 methylmethacrylate 200 500 800 400 ethyl methacrylate 200 450 ethyl acrylate190 100 n-butyl methacrylate 100 200 300 t-butyl methacrylate 200n-butyl acrylate 195 95 150 190 2-hydroxy ethyl 200 methacrylatemethacrylic acid 5 5 10 10 S P values 9.79 9.64 10.49 9.02 9.54

When the afore-mentioned substances having the SP values of 9.0 or moreare used as a dye migration preventive layer, the film thicknesspreferably is set from 1 μm to 100 μm, inclusive, more preferably from 2μm to 80 μm, inclusive and still preferably from 3 μm to 60 μm,inclusive. A thickness less than 1 μm leads to insufficient effects forpreventing the migration of the dye, and a thickness exceeding 100 μmmakes the film strength too high, thus degrading the suitability forattachment on a three-dimensional curved surface, so that such athickness is not preferable. Moreover, the cost also is increased, andsuch a thickness is not preferable from that respect also. Furthermore,when a glass transition temperature (Tg) of the afore-mentionedsubstances having the SP values of 9.0 or more applied to the dyemigration preventive layer is set at 60° C. or higher, preferably at 70°C. or higher and still preferably at 80° C. or higher, the molecularmovement can be frozen even at high temperatures such as in theoperation in the midsummer open air, and therefore such a configurationis more preferable.

As other effective forms of the dye migration preventive layer, a metalthin layer may be formed to be continuous with a colorable resin layeror to be continuous further with the dye migration preventive layer,which prevents the migration of the dye. This configuration, however, isnot preferable in the case where a retroreflective layer is formed at abottom layer. Herein, the metal layer may be formed of thebelow-described metals. Although its thickness may vary depending on themetal used, the thickness may be from 5 to 500 nm, preferably from 10 to400 nm and still preferably from 20 to 300 nm. The thickness of theafore-mentioned metal layer less than 5 nm cannot achieve the objectiveas the dye migration preventive layer, because the screening capabilityof the metal layer is not sufficient. Additionally, since the metallayer has to be stretched when the printing laminate is attached on acurved surface, the thickness of the metal layer further is decreased,thus worsening the condition. The thickness exceeding 500 nm, inversely,may degrade the adhesion of the metal layer with the colorable resinlayer or the dye migration preventive layer, or cracks may tend to occurin the metal layer, and the cost also is increased, and therefore such athickness is not preferable. A method for providing the afore-mentionedmetal layer is not limited especially, and general methods such asevaporation, sputtering, transferring and a plasma method are available.Among them, evaporation and sputtering are preferably used in terms ofthe workability. When the metal used for forming the metal layer also isnot limited especially, metals such as aluminum, gold, silver, copper,nickel, chrome, magnesium and zinc are available. Among them, in termsof the workability and the easiness of the formation the metal layer,aluminum, chrome and nickel are particularly preferable. The above metallayer may be formed of an alloy including two or more kinds of metals.

The provision of a surface resin layer on the colorable resin layer ofthe printing laminate of the present invention enables the protection ofthe dye in the colorable resin layer against ultraviolet rays, water andthe like, thus allowing the sufficient durability in the open air to bekept. Materials that can satisfy such required properties include olefinresins, i.e., polyethylene, polypropylene and the like, vinyl alcoholresins, i.e., polyvinyl alcohol and ethylene-vinyl alcohol copolymerresins, fluorine resins, silicon resins or a mixture of them and thelike.

Among them, synthetic resins containing fluorine resins and silicondenatured acrylic resins as main components, which have excellentoutdoor weathering resistance and rich non-affinity with the dye, areused preferably. The synthetic resins containing fluorine resins as amain component include fluorine resins such as polytetrafluoroethylene,tetrafluoroethylene-perfluoro alkylvinylether copolymer,tetrafluoroethylene-hexafluoropropylene copolymer,tetrafluoroethylene-hexafluoropropylene-perfluoro alkylvinylethercopolymer, tetrafluoroethylene-ethylene copolymer,polychlorotrifluoroethylene, chlorotrifluoroethylene-ethylene copolymer,polyvinylidene fluoride and polyvinyl fluoride. In order to processthese fluorine resins, a generally adopted method is to let the resinsmelt mainly by the application of heat and to process the resins in adesired shape, followed by cooling so as to form an article. However,the film produced by such a method is stretched in the longitudinaldirection and in the lateral direction, and therefore when thetemperature of the film is increased to 150 to 200° C. during thethermal transferring, the film tends to contract, thus increasing thetendency of occurring deficiencies such as blurring in printing and thelack of sharpness in printed pattern. In order to avoid thedeficiencies, the surface resin layer preferably is formed of anot-stretched fluorine resin film that is manufactured by a processingmethod such as solvent casting (casting) of a fluorine resin made offluoroolefin copolymer that is soluble in the afore-mentioned solvents.More preferably, the surface resin layer is formed by a reaction of afluoroolefin copolymer that is soluble in a solvent having a reactivefunctional group with a hardener and/or a catalytic hardener that reactwith this reactive functional group. Among them, in terms of theworkability for manufacturing the film, copolymers of fluoroolefins orcopolymers of fluoroolefins and a monomer other than the fluoroolefinsare particularly preferable because they have good solubility withrespect to general-purpose solvents (hereinafter, they are also referredto as “fluoroolefin copolymers”). Specific examples of fluoroolefinsused for preparing such fluoroolefin copolymers include: vinyl fluoride;vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,chlorotrifluoroethylene, hexafluoropropylene and the like. Thecopolymerization of two or more kinds of these fluoroolefins allows acopolymer containing fluoroolefins only as a monomer component to beobtained. Furthermore, the copolymerization of the afore-mentionedfluoroolefins with monomers that are capable of the copolymerizationwith them allows the preparation of a fluoroolefin copolymer that issoluble in a solvent. Specific examples of vinyl copolymers that arecapable of the copolymerization with the fluoroolefins include: alkyl orcycloalkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether,n-butyl vinyl ether, cyclohexyl vinyl ether and cyclopentyl vinyl ether;vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinylbutyrate, vinyl pivalate, vinyl versatate, vinyl benzoate, p-t-butylvinyl benzoate, cyclohexane vinyl carboxylate and isopropenyl acetate;monomers containing a hydroxyl group such as 2-hydroxy ethyl vinylether, 3-hydroxy propyl vinyl ether, 4-hydroxy butyl vinyl ether,2-hydroxy ethyl allyl ether and 2-hydroxy ethyl(meth)acrylate; monomerscontaining a carboxyl group such as acrylic acid and methacrylic acid;monomers containing an amino group such as N,N-dimethylaminoethyl(meth)acrylate and N,N-dimethylamino ethyl vinyl ether; monomerscontaining an epoxy group such as glycidyl vinyl ethers andglycidyl(meth)acrylate; monomers containing a hydrolyzable silyl groupsuch as trimethoxy vinyl silane, triethoxy vinyl silane, 2-trimethoxyethyl vinyl ether, γ-methacryloxy propyl trimethoxy silane; vinylmonomers containing a silyloxy group such as 2-trimethylsilyloxy ethylvinyl ether and 4-trimethylsilyloxy butyl vinyl ether; monomerscontaining silyloxy carbonyl group such as trimethylsilyl(meth)acrylate, vinyl-5-trimethyl silyloxy carbonyl pentanoate, inaddition to ethylene, propylene, vinyl chloride and variousalkyl(meth)acrylates. Among these monomers, in terms of copolymerizingproperties and coating properties, etc., the use of vinyl ester andvinyl ether without a functional group is preferable as an essentialcomponent. If required, the above-described monomers having a reactivefunctional group may be copolymerized.

A preferable copolymer of fluoroolefins and a monomer other thanfluoroolefins that is used for the present invention is obtained bycopolymerizing about 15 to 70 weight % of fluoroolefin, about 0 to 30weight % of vinyl monomer containing a reactive functional group andabout 5 to 85 weight % of another monomer that can be copolymerized withthem. A more preferable copolymer is obtained by copolymerizing about 20to 65 weight % of fluoroolefin, about 5 to 25 weight % of vinyl monomercontaining a reactive functional group and about 10 to 75 weight % ofanother monomer that can be co-polymerized with them. In the case of theusage of fluoroolefin less than about 15 weight %, the durability, theantifouling effects and the permeability of the sublimable dye becomeinsufficient, whereas in the case of the usage exceeding about 70 weight%, the solubility into general-purpose solvents would deteriorate, thusdegrading the workability, and therefore such usage is not preferable.As for the weight-average molecular weight of the copolymer used, interms of the workability and the durability of the film, a preferablerange is about 5,000 to 400,000 and a more preferable range is about7,000 to 300,000.

The fluorine resin that is the surface resin layer of the printinglaminate of the present invention can be prepared using a fluoroolefincopolymer and an acrylic polymer as described above. The acrylic polymermentioned here is a homopolymer or a copolymer whose essential componentis acrylic ester or metaacrylic ester, and those with or without theabove-described reactive functional group may be available. Althoughvarious known polymers are available as this acrylic polymer, in termsof the durability and the workability, it is preferable to use thepolymer with a weight-average molecular weight of about 5,000 to 400,000and more preferably about 7,000 to 300,000.

When the afore-mentioned fluoroolefin copolymer and acrylic polymer areused concurrently as the resin for the surface resin layer, the ratio byweight between the former and the latter is preferably in the range ofabout 30:70 to about 98:2 and more preferably in the range of about40:60 to about 95:5. In the case of the usage of the acrylic polymerless than about 2%, the properties of the acrylic polymer to be assignedwould not be exerted sufficiently, whereas in the case of the usageexceeding about 70 weight %, the durability, the antifouling effects andthe permeability of the sublimable dye would become insufficient, andtherefore such usage is not preferable.

When forming the surface resin layer of the printing laminate of thepresent invention, the fluoroolefin copolymer and the acrylic polymerare used in a state where they are dissolved in an organic solvent. Inthe case that the fluoroolefin copolymer or the acrylic polymer that ismixed therewith has a reactive functional group as described above, amaterial having a functional group that can react with the above-statedreactive functional group may be mixed therewith as a hardening agent.In the case of having a silyl group with hydrolyzability as the reactivefunctional group, a catalytic hardener made of acids, basic or variousorganic tin compounds may be mixed therewith. In addition, also in thecase that the hardening agent is mixed as described above, a catalystsuitable for promoting the hardening reaction may be added. As thehardening agent, in the case that the reactive functional group of thefluoroolefin copolymer is a hydroxyl group or a silyloxy group,polyisocyanate, block polyisocyanate, amino resin, metalalkoxide, metalchelate compounds or the like can be mixed. In the case that thereactive functional group is an epoxy group, polycarboxy compounds,polysilyloxycarbonyl compounds, polyamine compounds or the like can bemixed. In the case that the reactive functional group is a carboxylgroup or a silyloxycarbonyl group, polyepoxy compounds, epoxysilanecompounds, metal chelate compounds or the like can be mixed. In the casethat the reactive functional group is an amino group, polyepoxycompounds or epoxysilane compounds can be mixed as the hardening agent.When an amino resin is mixed as the hardening agent with thefluoroolefin copolymer or the mixture of a fluoroolefin copolymer and anacrylic polymer, about 5 to 100 parts by weight of amino resin, morepreferably about 10 to 60 parts by weight, is preferably mixed withabout 100 parts by weight of the above-described base resin component.

In the case where a hardening agent other than the amino resin is mixed,the hardening agent is mixed so that the functional group of thehardening agent constitutes preferably about 0.2 to 2.5 equivalentweight and more preferably about 0.5 to 1.5 equivalent weight withrespect to 1 equivalent weight of the reactive functional group in thefluoroolefin copolymer or the mixture of the fluoroolefin copolymer andthe acrylic polymer.

In the compositions used for forming the afore-mentioned surface resinlayer, fine particles of silica, calcium carbonate, aluminum hydroxide,acrylic resin, organic silicone resin, polystyrene, urea resin,formaldehyde condensate and the like may be added as a matting agent soas to decrease the 60° gloss of the surface to 70 or less, whereby thereflection of light equipment such as a fluorescent lamp on the surfacelayer can be prevented. The use of acrylic resin is preferable becausethe compatibility with the afore-mentioned fluoroolefin copolymersbecomes good.

In the compositions used for forming the afore-mentioned surface resinlayer and in the compositions used for forming the afore-mentioned dyemigration preventive colorable resin layer or the colorable resin layer,an ultraviolet absorber, a light stabilizer and an antioxidant may beadded and included individually or in the respective combination,whereby the long term durability further can be enhanced. As such anultraviolet absorber, known absorbers can be used, and typical onesinclude benzophenones, benzotriazoles, cyanoacrylates, salicylates andanilide oxalates. As the light stabilizer, hindered amines can be used,and as the antioxidant, known compounds such as hindered phenolcompounds, amine antioxidants and sulfur antioxidants can be used.Herein, the use of the ultraviolet absorber, the light stabilizer andthe antioxidant made of low molecular compounds would cause the problemssuch as the occurrence of phase caused by the phase separation fromtransparent resin, bleed-out, a volatilization phenomenon during a heattreatment performed for letting the sublimable dye penetrate the insideof the printing laminate, and therefore the use of high-molecular weighttype ultraviolet absorber, light stabilizer and antioxidant ispreferable.

The ultraviolet absorber used in the present invention includes, forexample: salicylic acids such as phenyl salicylate, p-di-tert-butylphenyl salicylate and p-octyl phenyl salicylate; benzophenones such as2,4-dihydroxy benzophenone, 2-hydroxy benzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxy benzophenone,2,2′-dihydroxy-4-methoxy benzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone and 2-hydroxy-4-methoxy-5-sulfo benzophenone;benzotriazoles such as 2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole and2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole; cyanoacrylatessuch as 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate andethyl-2-cyano-3,3′-diphenyl acrylate; metal oxides such as titaniumoxide, zinc oxide and cerium oxide, in addition to anilide oxalates,triazines, dibenzoylmethanes and benzylidenes.

As the ultraviolet absorber, a so-called high-molecular weight typeultraviolet absorber is available, in which the afore-mentionedultraviolet absorber is introduced in a part of a polymer.

As the high-molecular weight type ultraviolet absorber, known ones maybe used, including for example:

-   [2-hydroxy-4-(methacryloyloxyethoxy)benzophenone]-methyl    methacrylate copolymer,    [2-hydroxy-4-(methacryloyloxymethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4-(methacryloyloxyoctoxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4-(methacryloyloxydodecyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4-(methacryloyloxybenzyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′-dihydroxy-4-(methacryloyloxyethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′-dihydroxy-4-(methacryloyloxymethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′-dihydroxy-4-(methacryloyloxyoctoxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′-dihydroxy-4-(methacryloyloxybenzyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2-dihydroxy-4-(methacryloyloxydodecyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′,4-trihydroxy-4′-(methacryloyloxyethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′,4-trihydroxy-4′-(methacryloyloxymethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′,4-trihydroxy-4′-(methacryloyloxyoctoxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′,4-trihydroxy-4′-(methacryloyloxydodecyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2,2′,4-trihydroxy-4′-(methacryloyloxybenzyloxy)benzophenone]-methyl    methacrylate copolymer,-   [4-hydroxy-4′-(methacryloyloxyethoxy)benzophenone]-methyl    methacrylate copolymer,-   [4-hydroxy-4′-(methacryloyloxymethoxy)benzophenone]-methyl    methacrylate copolymer,-   [4-hydroxy-4′-(methacryloyloxyoctoxy)benzophenone]-methyl    methacrylate copolymer,-   [4-hydroxy-4′-(methacryloyloxydodecyloxy)benzophenone]-methyl    methacrylate copolymer,-   [4-hydroxy-4′-(methacryloyloxybenzyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4′-methyl-4-(methacryloyloxyethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4′-methyl-4-(methacryloyloxymethoxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4′-methyl-4-(methacryloyloxyoctoxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4′-methyl-4-(methacryloyloxydodecyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2-hydroxy-4′-methyl-4-(methacryloyloxybenzyloxy)benzophenone]-methyl    methacrylate copolymer,-   [2-(2′-hydroxy-4′-methacryloyloxyethoxy)benzotriazole]-methyl    methacrylate copolymer and-   [2-(2′-hydroxy-4′-methacryloyloxyethoxy)-5-chlorobenzotriazole]-methyl    methacrylate copolymer. Furthermore, a high-molecular weight type    ultraviolet absorber having a molecular weight of 500 or more, such    as    2,2′-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol],    also is preferable.

The light stabilizer functions so as to capture (couple with) radicalsgenerated due to ultraviolet rays with efficiency and inactivate thesame, whereby blocking the chain reaction to prevent the deteriorationof the dye. Examples of the light stabilizer include: various hinderedamines such as 4-benzoyloxy-2,2,6,6-tetramethyl piperidine,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butyl malonic acidbis(1,2,2,2,6-pentamethyl-4-piperidyl) andtetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4,-butane tetracarboxylate; hindered phenols such as2,4-di-tert-butylphenyl-3,5-di-tert-butyl-hydroxybenzoate; nickelcomplexes such as [2,2′-thiobis-(4-tert-butyl phenolate)]-tert-butylamine nickel (II) and [2,2′-thiobis-(4-tert-butyl phenolate)]-2-ethylhexyl amine nickel (II); nickel salts of phosphoric ester such as nickelsalt of 3,5-di-tert-butyl-4-hydroxy benzyl monoethyl ester phosphate.

Among them, a high molecular-weight type hindered amine light stabilizerhaving a molecular weight of 1000 or more is more preferable, whichincludes: a condensation polymer ofN,N,N′,N′,-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diaza decane-1,10-diamine,dibutylamine-1,3,5-triazine-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamineand N-(2,2,6,6 tetramethyl-4-piperidyl)butylamine; and a polymer of poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], dimethyl succinate and4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol.

As the antioxidant, there are two types including: a radical acceptortype in which protons are given to peroxides of generated radicals so asto stabilize the same; and a peroxide separation type in whichhydroperoxides are altered into stable alcohol. As the former, phenolcompounds and amine compounds are typical. As the phenol compounds,examples include: compounds such as hydroquinone and gallate; andhindered phenol compounds such as 2,6-di-tert-butyl-p-cresol,stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis(4-methyl-6-tert-butyl phenol), 2,2′-methylenebis(4-ethyl-6-tert-butyl phenol), 4,4′-thiobis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl phenyl)butane,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-4-hydroxybenzyl)benzene,tris(3,5-di-tert-butyl-4-hyrdoxybenzyl)isocyanurate, and tetrakis[methylene-3(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane. Asthe amine compounds, examples include N,N′-diphenyl-p-phenylene diamine,phenyl-β-naphthylamine, phenyl-α-naphthylamine,N,N′-β-naphthyl-p-phenylene diamine, N,N′-diphenyl ethylene diamine,phenothiazine, N,N′-di-sec-butyl-p-phenylene diamine,4,4′-tetramethyl-diamino diphenyl methane and the like

As the latter, sulfur compounds and phosphorus compounds are typical. Asthe sulfur compounds, examples include dilauryl thiodipropionate,distearyl thiodipropionate, lauryl stearyl thiodipropionate, dimyristylthiodipropionate, distearyl-β,β′-thiodibutyrate,2-mercaptobenzoimidazole and dilauryl sulfide. As the phosphoruscompounds, examples include: triphenyl phosphite, trioctadecylphosphite, tridecyl phosphite, trilauryl trithio phosphite, diphenylisodecyl phosphite, trinonyl phenyl phosphite and distearylpentaerythritol phosphite. Quencher is a compound that absorbsultraviolet rays and takes excitation energy from exited molecules so asto suppress the reaction of the excited molecules, and include variousknown metal complexes. Among these antioxidants and quencher, a hinderedphenol compound having a molecular weight of 1000 or more isparticularly preferable.

As the organic solvent, conventionally known solvent can be used.Specific examples include: esters such as ethyl acetate, butyl acetateand ethylcellosolve acetate; aromatic hydrocarbons such as toluene,xylene and ethylbenzene; aliphatic or alicyclic hydrocarbons such ashexane, heptane, octane, cyclohexane and ethylcyclohexane; alcohols suchas methyl alcohol, ethyl alcohol, isopropanol, n-butanol and isobutanol;and ketone solvent such as acetone, methyl ethyl ketone, methyl isobutylketone and cyclohexanone. Among them, when polyisocyanate compounds areused as the hardening agent, the use of the alcoholic solvent must beavoided. This is because an isocyanate group and alcohol react with eachother.

Specific examples of the silicon denatured acrylic resins are asfollows, which shows typical examples only:

-   (1) a cured film obtained by adding a hydrolytic catalyst to a vinyl    copolymer in which vinyl monomers having hydrolyzable silyl groups    are copolymerized;-   (2) a cured film obtained by adding a compound having both of an    epoxy group and a hydrolyzable silyl group in one molecule to a    vinyl copolymer in which vinyl monomers having amino groups and/or    carboxyl groups are copolymerized;-   (3) a cured film obtained by adding a polyisocyanate compound to a    vinyl copolymer having a hydroxyl group in which a silicon resin is    graft-polymerized; and-   (4) a cured film obtained by adding a hydrolytic catalyst to a vinyl    copolymer having a hydrolyzable silyl group in which a silicon resin    is graft-polymerized.

As the dye for sublimable ink used in the present invention, a dyehaving a property of sublimating or evaporating at the atmosphericpressure and at 70 to 260° C. is preferable. For example, dyes such asazo, anthraquinone, quinophthalone, styryl, diphenylmethane,triphenylmethane, oxazin, triazine, xanthene, methine, azomethine,acridine and diazine are available. Among them, 1,4-dimethylaminoanthraquinone, bromide or chloride1,5-dihydroxy-4,8-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1-amino-4-hydroxyanthraquinone,1-amino-4-hydroxy-2-(β-methoxyethoxy)anthraquinone,1-amino-4-hydroxy-2-phenoxy anthraquinone, methyl, ethyl, propyl andbutyl ester of 1,4-diaminoanthraquinone-2-carboxylic acid,1,4-diamino-2-methoxyanthraquinone, 1-amino-4-anilinoanthraquinone,1-amino-2-cyano-4-anilino(or cyclohexylamino)anthraquinone,1-hydroxy-2(p-acetaminophenylazo)-4-methylbenzene,3-methyl-4-(nitrophenylazo)pyrazolone, 3-hydroxyquinophthalone and thelike are available. As basic dyes, malachite green, methyl violet andthe like are available, and the use of a dye that is modified withsodium acetate, sodium ethylate, sodium methylate and the like ispreferable.

Using a sublimable ink using these dyes, printing is performed to atransfer paper or an ink temporary displaying surface layer that isprovided on a surface of a printing laminate by an electrophotographymethod, an electrographic recording method, an ink jet method, a thermaltransfer method or the like. Then, heat at about 100 to 200° C. isapplied to the printing laminate for about 10 seconds to several minutesusing a heat vacuum applicator, an oven drier, a far infrared heatingapparatus and the like. Herein, in the case of the transfer paper used,the heat is applied to the printing laminate while the printed surfaceof the sheet is applied to a surface of the printing laminate, and inthe case where the printing is conducted to the ink temporary displayingsurface layer, heating is conducted to the printing laminate as it is.Thereby, the sublimable dye is sublimated and a printed image isdiffused and dyed within the colorable resin layer. As a printing methodused in this step, known and common printing methods such as heattransfer printing, electrostatic printing, gravure printing, ink jetprinting and the like can be used, and, in particular, it is preferableto use an ink jet printer as the printing means, which enables fullcolor printing easily, and an on-demand type is preferable because thismethod is economical in terms of the usage efficiency of the ink.

Herein, the temperature of the heat treatment after the printingpreferably is in the rage of 150 to 200° C. in terms of the favorableworkability for carrying out the sublimation of the sublimable dye in ashort time without a significant thermal damage on a releasing film orthe like on a rear face of the printing laminate. Moreover, preferably,prior to the heat treatment, the printing surface may be dried to atacky-dry level, which makes the diffusion of the sublimable dye uniformduring the heat treatment. The transfer paper used in this step may be aprinting paper for ink jet that is commonly on the market, and ahydrophilic resin preferably is used for the ink temporary displayingsurface layer. Hydrophilic resins used for forming the above-describedtemporary display layer include, for example, a polyurethane resin, anacrylic resin, a fluororesin, unmodified or modified polyvinyl alcohol,polyester, acrylic urethane, a vinyl chloride maleic anhydridecopolymer, sodium salt of alkyl ester, gelatin, albumin, casein, starch,SBR latex, NBR latex, a cellulose resin, an amide resin, a melamineresin, polyacrylamide and polyvinyl pyrrolidone. These materials may becationic modified, or hydrophilic groups may be added to thesematerials, and one or more types of the thus prepared materials may beused.

Moreover, fillers such as silica, clay, talc, diatomaceous earth,zeolite, calcium carbonate, alumina, zinc oxide, titanium and the likemay be added thereto.

Note here that when the printing laminate of the present invention isapplied to the use for the attachment on a curved surface, for example,the laminate is required to have a sufficient stretching property. Alower molecular weight plasticizer and the like, however, are notsuitable for this application, because such a material would induce thebleed of the dye. Meanwhile, according to the present invention, theafore-mentioned dye migration preventive layer and the metal thin layercan prevent the bleed of the dye, and therefore a broad range of resins,i.e., resins having an excellent elongation percentage, can be selectedfor the rear-face side of the dye migration preventive layer and themetal thin layer without restrictions to the afore-mentioned resinssuitable for the dye migration preventive layer. More specifically, asmaterials satisfying such required properties, synthetic resins such asurethane resins, vinyl resins, acrylic resins, alkyd resins, polyesterresins, epoxy resins, fluorine resins, olefin resins, silicon resins andthe like are available. The dried film thickness of this layer in thisstep that has excellent flexibility is set at from 1 μm to 100 μm,inclusive, preferably from 3 μm to 80 μm, inclusive, and more preferablyfrom 5 μm to 60 μm. The film thickness less than 1 μm is not sufficientfor following the elongation during the stretching so as to prevent thebreakage of the dye migration preventive layer. Whereas, the filmthickness exceeding 100 μm makes the overall film thickness of the filmtoo large, which degrades the capability to follow the curved surfacewhen the film is attached to the board, and therefore such a range offilm thickness is not preferable. With this configuration, theelongation percentage of the laminate can be enhanced remarkably, andcracks, which would occur during the stretching of the dye migrationpreventive layer and the metal thin layer, can be prevented, resultingin a printing laminate that has excellent flexibility and elongationpercentage and that can prevent the bleed of the dye.

FIG. 1 is a cross-sectional view of a printing laminate according to oneembodiment of the present invention. This printing laminate is made upof: a surface resin layer (A)1 that has weak affinity with a sublimabledye and that has a permeability of the dye; and a dye migrationpreventive colorable resin layer (B)12 that has affinity with the dyeand prevents the migration of the dye, these layers being laminated inthis order from the surface of the laminate.

FIG. 2 is a cross-sectional view of a printing laminate according toanother embodiment of the present invention. This printing laminate ismade up of: a surface resin layer (A)1; a colorable resin layer (B1)2that has affinity with the dye; and a dye migration preventive layer(B2)3 for preventing the migration of the dye, the layers beinglaminated in this order from the surface of the laminate.

FIG. 3 is a cross-sectional view of a printing laminate according tostill another embodiment of the present invention. This printinglaminate is made up of: a surface resin layer (A)1; a colorable resinlayer (B1)2; a dye migration preventive layer (B2)3; and a flexibleresin layer (C)4 that has an elongation percentage larger than that ofthe dye migration preventive layer (B2)3, the layers being laminated inthis order from the surface of the laminate.

FIG. 4 is a cross-sectional view of a printing laminate according to afurther embodiment of the present invention. This printing laminate ismade up of: a surface resin layer (A)1; and a dye migration preventivecolorable resin layer (B)12, which are laminated in this order from thesurface of the laminate, and further is provided with an adhesive layer5 on a rear face of the dye migration preventive colorable resin layer(B)12 and a releasing member 6 below the adhesive layer 5. An antistatictreatment is applied to the adhesive layer 5 or the releasing member 6.

FIG. 5 is a cross-sectional view of a printing laminate according to astill further embodiment of the present invention. This printinglaminate is made up of: a surface resin layer (A)1; a colorable resinlayer (B1)2; a dye migration preventive layer (B2)3; and a flexibleresin layer (C)4 that has an elongation percentage larger than that ofthe dye migration preventive layer (B2)3, the layers being laminated inthis order from the surface of the laminate, and this printing laminatefurther is provided with an adhesive layer 5 on a rear face of theflexible resin layer (C)4 and a releasing member 6 below the adhesivelayer 5. An antistatic treatment is applied to the adhesive layer 5 orthe releasing member 6.

Note here that, in FIGS. 1 to 3 also, the adhesive layer 5 and thereleasing member 6 may be formed, and an antistatic treatment may beapplied to the adhesive layer 5 or the releasing member 6.

The printing laminate shown in FIG. 1 is formed by the following steps:in the first step, a coating of the surface resin layer 1 is applied ona supporting film such as a polyethylene terephthalate film or a castingsheet so that the dried film thickness becomes about 0.5 to 300 μm,preferably about 2 to 200 μm and more preferably about 3 to 100 μm,followed by drying at room temperature or by heating. Next, in thesecond step, a coating for the dye migration preventive colorable resinlayer 12 that follows the surface resin layer 1 is applied so that thedried film thickness becomes about 1 to 500 μm, preferably about 2 to400 μm, and more preferably about 3 to 300 μm, followed by drying atroom temperature or by heating.

The printing laminate shown in FIG. 3 is formed by the following steps:in the first step, a coating of the surface resin layer 1 is applied ona supporting film such as a polyethylene terephthalate film or a castingsheet so that the dried film thickness becomes about 0.5 to 300 μm,preferably about 2 to 200 μm and more preferably about 3 to 100 μm,followed by drying at room temperature or by heating. Next, in thesecond step, a coating for the colorable resin layer 2 that follows thesurface resin layer 1 is applied so that the dried film thicknessbecomes about 1 to 500 μm, preferably about 2 to 400 μm, and morepreferably about 3 to 300 μm, followed by drying at room temperature orby heating.

In the third step, a coating of the dye migration preventive layer 3that follows the colorable resin layer 2 is applied so that the driedfilm thickness becomes about 1 to 500 μm, preferably about 2 to 400 μmand more preferably about 3 to 300 μm, followed by drying at roomtemperature or by heating. In the fourth step, a coating for theflexible resin layer 4 that follows the dye migration preventive layer 3is applied so that the dried film thickness becomes about 1 to 100 μm,preferably about 3 to 80 μm, and more preferably about 5 to 60 μm,followed by drying at room temperature or by heating.

Note here that these steps can be conducted by applying the coating forthe flexible resin layer 4 in the first step, the coating for the dyemigration preventive layer 3 in the second step and the coating for thecolorable resin layer 2 in the third step and the coating for thesurface resin layer 1 in the fourth step. Furthermore, if required, theprocess excluding the flexible resin layer 4 can be carried out. Afterthe completion of these steps, the supporting film such as apolyethylene terephthalate film or a casting sheet is peeled off fromthe laminate and, if required, an adhesive layer or a glue layer may beformed on a rear face of the laminate, i.e., on a layer on the oppositeside of the surface resin layer, and moreover a releasing member such asa releasing paper or a releasing film may be attached to the adhesivelayer or the glue layer so as to complete the printing laminate. Herein,in the case where a biaxially stretched polyester film is used as thedye migration preventive layer 3, the afore-mentioned supporting filmdoubles as the dye migration preventive layer 3, and therefore the stepfor peeling the supporting film off from laminate can be omitted. Thedrying conditions after the application of the coatings in theafore-mentioned first, second, third and fourth steps may be determinedappropriately depending on the types of a base resin used as the coatingmaterial, the types of the functional group in the base resin, the typesof the reactive functional group in the base resin, the types of thehardening agent and the types of the solvent. The coating in each stepmay be applied by means of a spray, or a normally used coater such as aknife coater, a comma coater, a roll coater, a reverse roll coater and aflow coater. When a clear coating that does not contain a pigment isused as the coating used for forming each layer in the printing laminateof the present invention, a colorless printing laminate can be obtained.However, when a color coating that contains a pigment is used as thecoating for forming the surface resin layer and the lower layercontinuous with the layer, a colored printing laminate can be obtained.As the pigment used for obtaining the thus colored coating, knownpigments including: organic pigments such as copper phthalocyanine blue,copper phthalocyanine green, quinacridone red and hansa yellow;inorganic pigments such as ferric oxide red, ferric oxide yellow,titanium white, cobalt blue, carbon black and the like are suitable.Moreover, when “CHROMAFLAIR PIGMENT” (produced by Flex Products Inc.) isused, this pigment having a five-layered structure of the pigment itselfand generating interference wavelengths having spectral effects forvisualization such that incident light is reflected by about 50% at thesurface layer and by the remaining about 50% at theOPAQUE·REFLECTOR·METAL as the middle layer, different colors can bevisualized, and therefore such a configuration is preferable because aprinting laminate having an excellent designing ability can be obtained.The same effects can be obtained from “VARIOCROM” (trade name, producedby BASF Inc.) in which a surface of aluminum flake pigment is coatedwith iron oxide.

The configuration, in which a light diffusion layer with light diffusingfine particles mixed therein is formed in at least one layer of thesurface resin layer 1, the dye migration preventive colorable resinlayer 12, the dye migration preventive layer 3 and the lower layers ofthese, is preferable, because such a printing laminate of the presentinvention can be used as an internal illumination type film (a film forbacklight). In this case, the mixture of the light diffusing fineparticles in the lower layer side than the color layer is morepreferable, because the clarity and the coloring properties cannot beadversely affected.

The afore-mentioned light diffusing fine particles making up the lightdiffusion layer include for example: silica, calcium carbonate, titaniumdioxide, aluminum hydroxide, acrylic resin, organic silicone resin,polystyrene, urea resin, formaldehyde condensate and the like. Amongthem, at least one type may be selected, and they are not the limitingexamples.

As an optically transparent resin functioning as a binder of the lightdiffusion layer with the light diffusing fine particles dispersed andmixed therein, acrylic resins, polyurethane resins, polyester resins,polyvinyl chloride resins, polyvinyl acetate resins, cellulosic resins,polyamide resins, fluorine resins, polypropylene resins, polystyreneresins alone or in combination of them are preferable. Alternatively,each of the resins are three-dimensionally cured with a functional groupof a hardening agent such as a melamine resin, an isocyanate resin andan epoxy resin so as to form a resin composition, and the use of theresin composition is more preferable, which is not a limiting example. Afavorable difference in refractive index between the opticallytransparent resin and the light diffusing fine particles generally isabout 0.02 or more. Furthermore, Tg (glass transition temperature) ofthe optically transparent resin preferably is 50° C. or more, and Tgless than 50° C. would cause problems concerning a keeping quality dueto blocking when the light diffusion layer and other members contactwith each other, and therefore such temperatures are not preferable.

Among these resins, the use of acrylic resins, polyurethane resins,polyester resins, polyvinyl chloride resins and poly vinyl acetateresins alone or in combination of them are preferable, because they havean excellent dispersion suitability (wettability) of the light diffusingfine particles and controllability of the difference in refractiveindex. The use of a resin composition is more preferable, in which eachof the resins is three-dimensionally cured with a functional group of ahardening agent such as a melamine resin, an isocyanate resin and anepoxy resin.

The light diffusion layer may be manufactured as follows: an opticallytransparent resin and one or more types of light diffusing fineparticles are dissolved or dispersed in an appropriate organic solvent(or water), the resultant is applied using a general application methodsuch as roll coating and knife coating, followed by drying andevaporation of the organic solvent (or water), and furthermore, ifrequired, a curing reaction of the resin with a hardening agent may beadvanced. The application method may be selected appropriately dependingon the viscosity of the composition of the light diffusion resin, thetargeted thickness of the coating and the like. The amount of the lightdiffusing fine particles to be added preferably is 1 to 40 weight % withrespect to the optically transparent resin, and they may be dispersedand mixed depending on the required properties. The desirableapplication film thickness of the light diffusion layer is about 3 to 50μm in general, which is not limiting one.

According to the printing laminate having the afore-mentioned lightdiffusion layer function, when illumination light is incident from therear face of the laminate that is the opposite side of the surface resinlayer, light from a linear light source such as a fluorescent lamp ofbacklight can be diffused uniformly, which means a bright planarilluminant, and reflection on the surface by the fluorescent lamp on therear face also can be prevented. At this time, light passes through alsothe coloring layer in which printing has been conducted in the colorableresin layer using the sublimable dye, and therefore the function as theinternal illumination type signboard can be exerted. Herein, since thesublimable dye has a significantly good transparency, a large amount ofink should be used for printing in order to increase the transmittancedensity to a desired density. Therefore, the printing workabilitydeteriorates and a problem occurs concerning the drying properties afterthe printing. In order to cope with this problem, it was found that awhite pigment may be used in the layer subjected to the sublimabledyeing so as to function as a white layer, whereby the transmittancedensity of the printed image could be enhanced.

In this connection, in order to improve the sharpness, it was found thatthe formation of the white layer using a white pigment in at least onelayer of the afore-mentioned dye migration preventive colorable resinlayer 12, the colorable resin layer 2 and the dye migration preventivelayer 3 could enhance the transmittance density of the printed image.Herein, in the case where the dye migration preventive colorable resinlayer further is divided into a transparent resin layer as an upperlayer and a white layer as a lower layer, in addition to a colorableresin layer and a dye migration preventive layer, the colorable resinlayer further may be divided into a transparent resin layer as an upperlayer and a white layer as a lower layer. This configuration is morepreferable, because the sharpness of the image can be kept and thetransmittance density can be enhanced. Herein, a white pigment used forwhitening may be any one that is used normally for coloring syntheticresins in white, including, more specifically, titanium oxide, zincoxide, lead carbonate, barium sulfate, zinc sulfide, antimony oxide,specific titanates represented by MTiO₃ (M denotes at least one elementselected from the group consisting of Mg, Ca, Sr and Ba) and the like.The usage of the white pigment here preferably is set so that thetransmittance density V of the white layer (measured by densitymeasuring apparatus DM-201 produced by Noritsu Koki Co., Ltd.) is 0.10to 1.70, preferably 0.15 to 1.65 and more preferably 0.20 to 1.40. Thetransmittance density V of the white layer less than 0.10 would not besufficient for increasing the transmittance density of the image,whereas the transmittance density exceeding 1.70 would causeinsufficiency in the transmissivity of the light, thus degrading thecharacteristics of the internal illumination type signboard, andtherefore such a range of transmittance density is not preferable.

The configuration, in which a retroreflective structure described lateris manufactured in the lower layer continuous with the afore-mentioneddye migration preventive colorable resin layer 12, the lower layercontinuous with the dye migration preventive layer 3 or the lower layerof the flexible resin layer 4, is preferable for various advertisingsignboards including traffic signs, because, even in the nighttime, theillumination by a headlight of vehicles allows light to be reflectedprecisely in the direction of the light source, thus allowing a fullcolored image similar to the daytime to be visually recognized bydrivers of the vehicles. Furthermore, since the printing of an image inan on-demand method is enabled, there is no need to manufacture a plateper image, which is required for silk screen printing that is applied toa retroreflective sheet conventionally, and therefore this configurationis significantly effective for reducing the cost.

The following describes exemplary manufacturing methods (1) to (3) ofthe retroreflective sheet.

(1) As shown in FIG. 6, a focus resin composition, in which highrefractive glass beads 102 are mixed, is applied at a lower layer of theafore-mentioned respective resin layers so that an optimum dried filmthickness as a focus layer film 101 can be obtained, followed by dryingat room temperature or by heating. Herein, although the optimum driedfilm thickness of the focus layer may vary according to the particlediameter of the glass beads, the film thickness may be about 10 to 70μm. Next, a reflective layer made of a metal reflective layer 103 isformed. Preferable coating used here for the focus resin compositioncontains as a base polymer composition polyurethane resins, polyvinylacetal resins, acrylic resins, alkyd resins, polyester resins and thelike. These resins may be used as a non cross-linking type or may beused as a thermosetting type by mixing a hardening agent such as aminoresins, epoxy resins and polyisocyanate, block polyisocyanate.

Furthermore, drying conditions after the application of the coating forthe focus resin composition in the above may be determined appropriatelydepending on the types of a base resin used as the coating material, thetypes of the reactive functional group in the base resin, the types ofthe hardening agent and the types of the solvent.

Preferably glass beads used here have a refractive index of 1.90 to 2.40and more preferably 2.10 to 2.30. The particle diameter thereofpreferably is from 5 to 300 μm, more preferably from 20 to 100 μm. Theparticle diameter of the beads less than 5 μm would make the requiredfilm thickness of the focus layer too small, thus making it difficult tocontrol the film thickness. Whereas, the particle diameter exceeding 300μm would make the required film thickness of the focus layer too large,thus making it difficult to shape the resin concentrically with thespherical diameter of the glass beads, which is due to the flow of theresin during heating for the shaping. The refractive index less than 1.9would make the required film thickness of the focus layer too large,thus making it difficult to shape the resin concentrically with thespherical diameter of the glass beads. In addition, it is extremelydifficult to manufacture industrially the beads having a refractiveindex exceeding 2.4 so as to prevent the crystallization and formtransparent glass beads precisely.

A method for providing the afore-mentioned metal reflective layer 103 isnot limited especially, and normally used methods such as sputtering,transferring and a plasma method are available. In particular, in termsof the workability, evaporation and sputtering are preferably used.Metals used for forming such a metal layer also are not limitedespecially, and metals such as aluminum, gold, silver, copper, nickel,chrome, magnesium and zinc are available. Among these metals, in termsof the workability, the easiness of the formation of the metalreflective layer, the durability of reflective efficiency of light andthe like, aluminum, chrome and nickel are particularly preferable. Theabove metal reflective layer may be formed of an alloy including two ormore kinds of metals. Although its thickness may vary depending on themetal used, the thickness may be from 5 to 200 nm, preferably from 10 to100 nm. The thickness of the afore-mentioned metal reflective layer lessthan 5 nm cannot achieve the objective as the reflective layer, becausethe screening capability of the metal reflective layer is notsufficient. The thickness exceeding 200 nm, inversely, may cause thetendency to generate cracks in the metal reflective layer and the costalso is increased, and therefore such a thickness is not preferable.

(2) As shown in FIG. 7, a coating for forming a glass beads fixing layer201 is applied at a lower layer of the afore-mentioned respective resinlayers so that the dried film thickness of the glass beads fixing layer201 is in the range of 100 μm from the thickness of 10% of the glassbeads particle diameter used, preferably in the range of 80 μm from thethickness of 20% of the glass beads particle diameter used, followed bydrying at room temperature or by heating so as to allow a solvent toevaporate. Next, high refractive glass beads 202 are embedded therein.Typical coatings used for forming the glass beads fixing layer include amixture of fluoroolefin copolymers containing a reactive functionalgroup, polyester resins, alkyd resins, polyurethane resins, acrylicpolymers having a reactive functional group as a base resin componentwith a hardening agent and/or a hardening catalyst such as amino resins,epoxy resins, polyisocyanate and block polyisocyanate. Herein, theafore-mentioned base resin component may be used alone or as a mixtureof two or more types. As the application form, a solution type, a nonwater dispersion type, a water soluble type and a water dispersion typecan be all available, and a solution type is particularly preferable.

Next, the coating for the focus resin composition described in the above(1) is applied so as to obtain an optimum dried film thickness as thefocus layer film 203, followed by drying at room temperature or byheating.

The coating in each step in the above may be applied by spray coating,or a normally used coater such as a knife coater, a comma coater, a rollcoater, a reverse roll coater and a flow coater.

When a clear coating that does not contain a pigment is used as thecoating used for forming each layer in the retroreflective sheet of thepresent invention, a colorless retroreflective sheet can be obtained.Alternatively, when a color coating that contains a pigment is used asthe coating for forming the respective layers in FIG. 6 and FIG. 7, acolored retroreflective sheet can be obtained as well. As the pigmentused for obtaining the thus colored coating, known and conventionalpigments including: organic pigments such as copper phthalocyanine blue,copper phthalocyanine green, quinacridone red and hansa yellow;inorganic pigments such as ferric oxide red, ferric oxide yellow,titanium yellow and cobalt blue and the like can be used.

For the thus obtained retroreflective sheet of the present invention,after the formation of the metal reflective layer 204 as describedabove, an adhesive layer or a glue layer may be formed on the laminationof the metal reflective layer, and moreover, if required, a releasingmember such as a releasing paper or a releasing film may be attachedthereto so as to form a final product.

(3) As shown in FIG. 8A, a plurality of transparent glass beads 302 areembedded in the planar form at the surface of a glass beads temporaryfixing layer 307 made of polyethylene that is laminated on a polyesterfilm 308. Heat is applied to a polyethylene laminate film (the glassbeads temporary fixing layer 307 and the polyester film 308) so as tosoften the polyethylene, whereby the glass beads 302 are embedded. Theseglass beads 302 are fine particles having a particle diameter of about 5to 300 μm and a refractive index of about 1.8 to 2.1. In particular,preferable glass beads have a refractive index of about 1.9 to 1.95(particularly preferably, 1.92 to 1.93) and a particle diameter of about20 to 90 μm (particularly preferably, 40 to 80 μm).

Next, a metal reflective layer 303 is formed by evaporation on thehemispherical faces of the glass beads 302 that are exposed from thesurface of the afore-mentioned glass beads temporary fixing layer 307.This evaporation is performed to the entire surface of the glass beadstemporary fixing layer 307. Then, the metal reflective layer 303 that isevaporated to the portions other than the glass beads 302 on the surfaceof the glass beads temporary fixing layer 307, which will be describedlater, remains on the surface of the glass beads temporary fixing layer307 as it is, and the other portions of the metal reflective layer 303are transferred to a supporting resin sheet 304 together with the glassbeads (FIG. 8E). As the afore-mentioned metal reflective layer 303, analuminum reflective layer is preferable, and layers made of other metalssuch as gold, silver, copper, nickel and chrome are applicable.

As the next step, a method for manufacturing a retroreflective sheethaving the following two types of structures may be carried out:

-   (A) a type with a primer layer 305; and-   (B) a type without a primer layer

In the case of the above (A), an adhesive layer is laminated on a rearface of the primer layer 305, and in the case of the above (B), anadhesive layer is laminated on a rear face of the supporting resin sheet304. In order to adjust the glass beads transferring capability of thesupporting resin sheet in which the glass beads in the glass beadstemporary fixing layer are to be transferred and embedded, a highpolymer or a low molecular plasticizer or the like should be used as thesupporting resin sheet in some cases. Such a plasticizer might transferto the interface between the adhesive and the supporting resin sheet orthe adhesive layer with the passage of time and degrade the propertiesof the adhesive. That is, the adhesion of the interface between theadhesive and the supporting resin sheet, the adhesion properties of theadhesive to the board and the like might deteriorate. In order to solvethese problems, i.e., to prevent the transferring of the plasticizerfrom the supporting resin sheet to the adhesive layer, the primer layermay be laminated in some cases.

Regarding the type (A) having the primer layer 305, resins having anexcellent interlayer adhesion with the supporting resin sheet may beselected as a resin for the primer layer 305 from resins having theafore-mentioned functional groups or hardening agents having functionalgroups reacting with these resins and with the functional groups ofthese resins. Then, a solution of the thus selected resin for the primerlayer 305 is coated on a polyester film 306 that is prepared separately,followed by drying using a hot air dryer. The thickness of the primerlayer 305 in this step may be 3 μm to 100 μm, preferably 6 μm to 50 μm.The thickness less than 3 μm is not preferable, because the effect forpreventing the migration of the plasticizer or the like woulddeteriorate, whereas the thickness exceeding 100 μm is not preferable,because the workability of the attachment of the reflective sheet andthe like would deteriorate.

Following this, the supporting resin sheet 304 having a uniformthickness of about 10 to 300 μm, preferably about 30 to 100 μm, ismanufactured on the primer layer 305 formed as above (FIG. 8B). Asresins applicable to this supporting resin sheet 304, resins having theafore-mentioned functional groups are preferable.

The type (B) that does not have the primer layer 305 can be implementedby the afore-mentioned manufacturing method of the retroreflective sheetin which the steps for forming the primer layer are omitted. Next, asshown in FIG. 8C, the supporting resin sheet 304 as stated above isbrought along the surface of the glass beads temporary fixing layer 307.Then, as shown in FIG. 8D, pressure is applied to the supporting resinsheet 304 toward the surface of the glass beads temporary fixing layer307. The pressure is applied so that the hemispherical faces of theglass beads 302 with the metal reflective layer 303 evaporated thereoncan be embedded in the supporting resin sheet 304. In this step, inorder to increase the fixing force of the glass beads 302 with thesupporting resin sheet 304, it is effective to further add a couplingagent or the like to the supporting resin sheet 304. Then, as shown inFIG. 8E, the polyester film 308 together with the glass beads temporaryfixing layer 307 are peeled off from the surface of the supporting resinsheet 304. In this step, as shown in FIG. 8E, the glass beads 302 remainin the supporting resin sheet 304 so that the hemispheres remainembedded in the supporting resin sheet 304. After that, in the casewhere the curing form in which the reaction proceeds at room temperature(e.g., isocyanate curing) is applied to the primer layer and/or thesupporting resin sheet, an aging treatment preferably is performed inthe environment at 30 to 40° C. to finish the reaction substantially, inorder to remove variations in properties of the connecting portionsduring the following shaping process by heating and in order tostabilize the self-sustaining form after the process. Furthermore, inorder to enhance the adhesion property between the glass beads and thesupporting resin sheet, it is effective to perform a heat treatment at120 to 150° C.

Next, the surface of the supporting resin sheet formed in the stateshown in FIG. 8F is covered with the dye migration preventive colorableresin layer 12 of the printing laminate or the dye migration preventivelayer 3 or the flexible resin layer 4 of the same. FIG. 8F shows theexample covered with the flexible resin layer 4. Thermo compressionshaping is performed using a patterned emboss roll 309 from therear-face polyester film side 306 of the supporting resin sheet 304 inwhich the resin layer is disposed (FIG. 8G). As means for this thermocompression shaping, it is preferable to allow a heated roll whosesurface temperature is at 150 to 240° C., preferably at 170 to 220° C.to pass through. A supporting resin sheet capable of beingthermo-compression shaped at a temperature less than 150° C. andexhibiting adhesion with the surface film is not preferable, becausesuch a sheet cannot keep the self-sustaining form for a long time. Asupporting resin sheet capable of being thermo-compression shaped at atemperature exceeding 240° C. also is not preferable, because such asheet would cause a deterioration in the workability during the shapingby heating, for example, a polyester film used as a protective film maymelt during the shaping by heating.

After the shaping by heating, the rear-face polyester film 306 is peeledoff, so as to manufacture a raw fabric of a high-brightnessretroreflective sheet. Thereby, an emboss groove 310 having a width of200 to 800 μm and a depth of 100 to 150 μm, for example, is formed onthe rear face side of the supporting resin sheet 304.

An adhesive layer or a glue layer may be formed so as to cover theemboss groove, and moreover, if required, a releasing member such as areleasing paper or a releasing film may be attached to the adhesionlayer or the like so as to form a final product.

As the retroreflective sheet that is located at the lower layer of theprinting laminate of the present invention, various knownretroreflective sheets can be applied in addition to the afore-mentionedretroreflective sheet.

In the printing laminate according to the present invention obtainedthrough the afore-mentioned process, also in the case of the structureother than the afore-mentioned retroreflective sheet, the dye migrationpreventive layer 3, the flexible resin layer 4 or a metal evaporationfilm may be formed on the opposite of the surface side, and thereafter,if required, an adhesive layer or a glue layer may be laminated on theselayers and a releasing member such as a releasing paper or a releasingfilm may be attached to the adhesive layer or the glue layer so as toform a finished product of the printing laminate. The releasing memberused herein may include an antistatic agent added by kneading or anantistatic agent may be applied on the surface of the releasing memberin order to reduce an electrical resistance of the surface of thereleasing member, thus preventing the generation of static electricity.This configuration is preferable, because instability of a printedimage, caused by fluctuations in the discharge direction of an ink froma nozzle for printing, can be prevented, which results from the staticelectricity generated when the sheet is wound off or the staticelectricity generated by the friction between the printing laminate anda printer during the printing by an ink jet printer. The antistaticagents used herein include various surface-active agents, inorganicsalts, polyhydric alcohols, metal compounds, carbons and the like. Forinstance, as the surface-active agents, various surface-active agentsincluding: anionic antistatic agents such as alkyl sulfonates,alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ethoxy sulfateester salts and alkyl phosphoric ester salts; cationic antistatic agentssuch as alkyl trimethyl ammonium salts, acyloylamidopropyl trimethylammonium methosulfate, alkyl benzyl dimethyl ammonium salts and acylcholine chloride; amphoteric antistatic agents such as alkyl betainetypes, alkyl imidazoline types and alkyl alanine types; and nonionicantistatic agents such as fatty acid alkylolamide,di-(2-hydroxyethyl)alkylamine, polyoxyethylene alkylamine, fatty acidglycerin ester, polyoxyethylene fatty acid glycol ester, fatty acidsorbitan ester, polyoxy fatty acid sorbitan ester, polyoxyethylenealkylphenyl ether and polyoxyethylene alkyl ether are included. In thecase where the releasing member 6 is a polyethylene terephthalate, 5weight % of polyethylene glycol may be copolymerized during the polymersynthesis, for example.

Note here that, as the afore-mentioned releasing member, a biaxiallystretched polyester film to which anneal processing has been conductedby heating beforehand preferably is applied as a base film, and abiaxially stretched polyester film whose shrinkage ratio is 1.0% or lessin the winding direction of the film when heat is applied at 150° C. for30 minutes, preferably 0.8% or less, and more preferably 0.6% or less isapplied preferably as the base film. The releasing member with ashrinkage ratio exceeding 1.0% makes the printing laminate curled towardthe releasing member side when the printing laminate of the presentinvention is heated for sublimation dyeing.

Furthermore, if required, a coating formation composition including fineparticles made of hydrotalcites represented by [M²⁺ _(1-X)M³⁺_(X)(OH)₂]^(X+)[A^(n−) _(X/n).mH₂O]^(X−)(M²⁺denotes divalent metal ions,M³⁺ denotes trivalent metal ions, A^(n−) denotes anions, 0<X≦0.33, 0≦m≦2and metal oxides may be applied to the surface resin layer 1, followedby drying. Thereby, a coating exhibiting affinity for water can beformed, which means the formation of a firmly constructed surface havinga sufficiently small contact angle for water, thus preventing thecontamination due to the affinity for water and preventing the adhesionof waterdrops due to condensation, which impairs the retroreflectiveeffect, and therefore sufficient retroreflective capability can besecured in the nighttime. Thus, this configuration is suitable for theapplications to various advertising signboards including traffic signs.Furthermore, the above compositions are significantly preferable,because they can exhibit the water affinity properties with a filmthickness of 1 μm or less and can keep the long-term water affinityproperties in the open air and when a sublimable dye is allowed topenetrate from the surface resin layer into the printing laminate, thepenetration of the dye is not hindered. As the fine particles of themetal oxides, titanium oxide particles, in particular a slurry solutionof titanium oxide, are the most preferable. However, instead of titaniumoxide, transition metal oxides such as zirconium oxide, strontiumtitanate, tungstic oxide, iron oxide and the like and other metal oxidessuch as zinc oxide, bismuth oxide, tin oxide, alumina, magnesia andstrontium oxide also can be used. The average particle diameterpreferably is within the range of 0.001 to 0.5 μm, and particularlypreferably 0.01 to 0.1 μm.

Furthermore, if required, a temporary displaying surface layer withreleasing properties may be laminated on the surface side of theprinting laminate. The temporary displaying surface layer herein may bemanufactured by applying a resin for the temporary displaying surfacelayer using the afore-mentioned application apparatus so that the driedfilm thickness becomes about 1 μm to 100 μm, preferably about 3 μm to 80μm and more preferably about 5 μm to 60 μm. Moreover, if required, thetemporary displaying surface layer may be manufactured to include alamination film of two or more layers. In that case, this layer can bemanufactured by laminating the layers from the lower layer to the upperlayer sequentially. Note here that, in this case, the uppermost side ofthe temporary displaying surface layer preferably is made of a resinhaving absorbing properties of an ink containing a sublimable dye andthe layer on the side contacting with the surface resin layer(A)preferably is made of a resin having non-affinity with the sublimabledye.

Above all, according to the printing laminate of the present inventionin which the temporary displaying surface layer is laminated on thesurface side, an image photographed by a commercially available digitalcamera can be printed directly on the temporary displaying surface layerof the printing laminate, and the following heat treatment at 150 to200° C. for several minutes allows the sublimable dye printed in thetemporary displaying surface layer to diffuse and penetrate the insideof the printing laminate, thus forming an image easily. This image has ahigh resolution equal to a conventional silver-halide photograph, and asa result of the 1000-hour test using a sunshine carbon type acceleratedweathering tester specified by JIS Z 9117 (which equals atmosphericexposure test, facing to the south at right angles, for 5 years), theimage showed a high durability such that it was free from abnormalitiesand fading was hardly recognized. This would equal the storage stabilitywithin doors for the time period far exceeding 100 years, and comparedwith a picture by a conventional silver-halide photograph or a widelyavailable aqueous ink jet printer, a larger size image can be producedat a lower cost than the conventional one. Furthermore, the disposal ofa developer, which is required for silver-halide photograph, becomesunnecessary, and therefore a photographed image that is moreenvironmental friendly and is significantly sharp with high durabilityand high storage stability can be obtained.

As a method for implementing the heating and diffusing printing in thisstep, an indirect heating method and a direct heating method areavailable. The indirect method includes heating by hot air, heating byirradiation with far infrared radiation and the like, and the directmethod includes a method for bringing the printing laminate in directcontact with a heating plate, for winding the printing laminate around aheated roll and the like. Either of these heating methods can beselected, or these methods may be used concurrently. Although heating athigh temperatures of 150 to 200° C. is required for the diffusiondyeing, if the temperature of the printing laminate itself is increasedrapidly to the afore-mentioned high temperatures, the rapid thermalexpansion of the sheet occurs, thus generating the abnormalities in theappearance of the sheet such as wrinkles, and therefore such a processis not preferable. As a result of keen examinations by the inventors ofthe present invention in order to cope with these problems, heat may beapplied in the order of the initial heating at 70 to 130° C., followedby at 120 to 150° C., and in the case where the temperature further isto be increased, followed by 140 to 200° C., and then the temperaturemay be decreased as in at 120 to 150° C., followed by at 70 to 130° C.and at room temperature. In this way, when the diffusion printing isconducted in a cycle of the rise of the temperature sequentially withthermal gradient, heating at a constant temperature and the fall of thetemperature, the contraction of the sheet due to the thermal expansionand the temperature fall can be alleviated, so that abnormalities in theappearance such as wrinkles do not occur, and therefore such a conditionis preferable. Furthermore, preferably, the initial rise of thetemperature takes 10 to 60% of the total heating time, the heating at aconstant temperature takes 20 to 80% of the total heating time and thefall of the temperature takes 10 to 40% of the total heating time. Morepreferably, the initial rise of the temperature takes 15 to 35% of thetotal heating time, the heating at a constant temperature takes 30 to70% of the total heating time and the fall of the temperature takes 15to 35% of the total heating time. Moreover, in the case of heating withrolls, the use of a cambered roll whose central portion is thicker thanboth end portions is preferable for the process of the fall of thetemperature, because this can prevent wrinkles that are generated causedby the contraction of the sheet during the fall of the temperature. Thegradient of the cambered roll used here preferably is set so that adifference in diameter per width of 1000 mm between the both endportions and the central portion becomes 0.5 to 10 mm, preferably 1 to 5mm. In the case of the indirect heating, preferably, at the entrance ofa heater, a sheet may be sandwiched between upper and lower two rollsand may be transferred sequentially by a lower support guide roll thatis driven, and if required, an upper press roll may be provided at somemidpoint of the transferring to sandwich the sheet in order to assistthe smooth transferring of the sheet. In this way, the indirect heatingis preferable because this allows a required quantity of the printinglaminate to be heated without loss. In the case where a separate sheetis to be heated, the sheet may be left on a heated plate heated at arequired temperature. Herein, in the case where consecutive processingis carried out using a heated roll, in addition to the afore-mentionedconditions, the tension for winding may be set at 5 to 40 kg/m width,preferably at 10 to 30 kg/m width, which can prevent wrinkles occurringin the sheet. The tension less than 5 kg/m width would cause wrinklesduring the winding, and the tension exceeding 40 kg/m width appliesunnecessary stretching to the sheet, and therefore such a range oftension is not preferable.

WORKING EXAMPLES

The present invention will be described more specifically by way of thefollowing Working Examples. In the following Working Examples, “parts”refer to parts by weight, and “%” refers to percentage by weight.

Working Example 1

When preparing a resin composition for the surface resin layer 1 shownin FIG. 1, a resin composition containing: about 100 parts of a solutionof a copolymer of hexafluoropropylene/ethylvinylether/VEOVA9/monovinyladipate=50/15/20/15 (weight percentage), which had the weight averagemolecular weight of about 45000, as a fluorine resin (“VEOVA9”: tradename produced by Japan Epoxy Resins Co., Ltd., vinylester of branchedfatty acid, the solvent is a mixture solvent of toluene/n-butanol=70/30(weight percentage), containing non-volatile matter of about 50%); about7.4 parts of sorbitol polyglycidylether having an epoxy equivalent of170; about 0.6 part of diaza-bicyclo-octane; about 1 part of TINUVIN900(produced by Ciba Specialty Chemicals Inc., benzotriazole basedultraviolet absorber); and about 1 part of TINUVIN292 (produced by CibaSpecialty Chemicals Inc., hindered amine based light stabilizer) wasapplied on a polyester film so as to have a dried film thickness ofabout 20 μm, followed by drying by heating at about 140° C. for about 10minutes to obtain the surface resin layer 1. Following this, on the thusmanufactured surface resin layer 1, a resin composition, in which about100 parts of the vinyl copolymer (a-1) synthesized in theafore-mentioned Reference Example 1; and about 25 parts of BURNOCKDN-950 as a hardening agent (polyisocyanate prepolymer produced byDainippon Ink and Chemicals, Inc., containing non-volatile matter ofabout 75%) were mixed, was applied to have a dried film thickness ofabout 30 μm, followed by drying by heating at about 140° C. for about 10minutes to manufacture a dye migration preventive colorable resin layer12. On the surface of the thus obtained dye migration preventivecolorable resin layer 12 of the printing laminate, as shown in FIG. 4, amixture solution including: about 100 parts of FINETAC SPS-1016 as anacrylic adhesive (produced by Dainippon Ink and Chemicals, Inc.,); andabout 2 parts of FINETAC TA-101-K as a cross-linking agent (produced byDainippon Ink and Chemicals, Inc., hardening agent for adhesives,chelate type) was applied, followed by drying by heating at about 100°C. for about 5 minutes to form an adhesive layer 5 having a thickness ofabout 35 μm. Furthermore, a releasing film 6 made of a biaxiallystretched polyester releasing film having a thickness of 50 μm whose oneside was coated with silicon and the other side was subjected toantistatic finish and further annealed (produced by Teijin DuPont FilmsJapan Limited, trade name: A-31, having a shrinkage ratio of 0.4% in thewinding direction of the film when heated at 150° C. for 30 minutes) wasattached to this adhesive layer 5, and thereafter the polyester film asthe supporting film was peeled off so as to form a final product.

Next, an image was printed on a transfer paper (Gradess S-coat Paper) bya piezo-type printer, which was a kind of ink jet method printersseparately prepared (by Mutoh Industries Ltd. RJ-6000). An ink forsublimable ink jet used here was produced by Kiwa Chemical Ind. Co.,Ltd., which contained a sublimable dye (a set of six colors includingcyan, magenta, yellow, black, light cyan and light magenta). The printedsurface of the transfer paper was applied to the surface resin layer 1of the printing laminate manufactured as above, and heat and pressurewere applied using a heat vacuum applicator (HUNT EUROPE, VacuSeal 4468)at the setting temperature of about 170° C. for about 7 minutes and atthe degree of vacuum of 3.99×10³ Pa (30 mmHg), whereby heat was appliedto both of the printing laminate and the transfer paper so as to allowthe diffusion and the dyeing of the image printed on the transfer paperinto the printing laminate and the transfer of the image into the dyemigration preventive colorable resin layer 12.

Working Example 2

For the preparation of a resin composition for the surface resin layer 1shown in FIG. 2, FLUONATE K-703 (produced by Dainippon Ink andChemicals, Inc., weight average molecular weight of 40000, solid contenthydroxyl value of 72, containing non-volatile matter of about 60%) wasused as a fluorine resin, BURNOCK DN-950 was used as a hardening agent,TINUVIN 900 was used as an ultraviolet absorber, and TINUVIN 292 wasused as an antioxidant. The mixture ratio of the resin composition forthe surface resin layer 1 in this Working Example 2 was as follows:about 100 parts of FLUONATE K-703, about 25 parts of BURNOCK DN-950,about 1 part of TINUVIN 900 and about 1 part of TINUVIN 292 were used.Then, the afore-mentioned composition was applied on a polyester film tohave a dried film thickness of about 20 μm, followed by drying byheating at about 140° C. for about 10 minutes, whereby the surface resinlayer 1 was obtained. Following this, on the thus manufactured surfaceresin layer 1, polycarbonate based non-yellowing type urethane resinNY-331 (produced by Dainippon Ink and Chemicals, Inc., containingnonvolatile matter of about 25%, solvent: DMF, 100% modulus: about 55kg/cm²) was applied to have a dried film thickness of about 20 μm,followed by drying by heating at about 140° C. for about 10 minutes soas to form a colorable resin layer 2. Following this, on this colorableresin layer 2, a resin composition, in which about 100 parts of vinylpolymer (a-2) that was synthesized according to Reference Example 2described above, and about 50 parts of BURNOCK DN-950 as a hardeningagent were mixed, was applied so as to have a dried film thickness ofabout 15 μm, followed by drying by heating at about 140° C. for about 10minutes, whereby a dye migration preventive layer 3 was manufactured.Following this, on this dye migration preventive layer 3, a resincomposition, in which about 100 parts of ACRYDIC 49-394-IM as an acrylicresin (produced by Dainippon Ink and Chemicals, Inc., containingnonvolatile matter of about 50%) and about 15 parts of BURNOCK DN-950were mixed, was applied to have a dried film thickness of about 20 μm,followed by drying by heating at about 140° C. for about 10 minutes,whereby the flexible resin layer 4 was obtained.

On the surface of the flexible resin layer 4 of the thus obtainedprinting laminate, as shown in FIG. 5, an adhesive layer 5 and areleasing film 6 were formed in a manner similar to Working Example 1 toform a final product.

Next, a printed surface of a transfer paper was applied to the surfaceresin layer 1 so as to transfer an image into the colorable resin layer2 in a manner similar to Working Example 1.

Working Example 3

The configuration, the dimensions and the manufacturing method weresimilar to Working Example 2 except that the mixture liquid of the resincomposition for the surface resin layer 1 and the mixture liquid for thecolorable resin layer 2 were changed as follows. According to thisWorking Example, the resin composition for the surface resin layer 1 wasmixed for example to include: about 100 parts of FLUONATE K-700(produced by Dainippon Ink and Chemicals, Inc., weight average molecularweight of 70000, solid content hydroxyl value of 48, containingnon-volatile matter of about 50%); about 15 parts of SUMIMAL M-100C. asa hardening agent (methylated melamine resin produced by SumitomoChemical Co., Ltd., containing non-volatile matter of 100%); about 1.3parts of NACURE 3525 as a hardening catalyst (produced by KingIndustries, Inc., dinonyl naphthalene disulfonic acid); about 1 part ofTINUVIN 900 and about 1 part of TINUVIN 292.

The resin composition for the colorable resin layer 2 was mixed forexample to include: about 100 parts of BURNOCK D6-439 (alkyd resinproduced by Dainippon Ink and Chemicals, Inc., solid content hydroxylvalue of 140, containing non-volatile matter of about 80%); and about 82parts of BURNOCK DN-980 as a hardening agent (polyisocyanate prepolymerproduced by Dainippon Ink and Chemicals, Inc., containing non-volatilematter of about 75%).

Working Example 4

The configuration, the dimensions and the manufacturing method weresimilar to Working Example 2 except that the mixture liquid of the resincomposition for the surface resin layer 1 was changed as follows.According to this Working Example, the resin composition for the surfaceresin layer 1 was mixed for example to include: about 100 parts ofACRYDIC A-9521 (silicon acrylic resin produced by Dainippon Ink andChemicals, Inc., solid content of 50%) and about 22 parts of ACRYDICHZ-1018 as a hardening agent (epoxy group containing silicon compoundproduced by Dainippon Ink and Chemicals, Inc., solid content of 55%).

Working Example 5

The configuration, the dimensions, the manufacturing method and the likewere similar to Working Example 2 except that a peelable temporarydisplaying surface layer capable of displaying by printing was laminatedon the printing laminate. On the surface resin layer 1 of the printinglaminate manufactured by Working Example 2, FLUONATE FEM-600 produced byDainippon Ink and Chemicals, Inc., (solid content of 45%) was applied tohave a dried film thickness of about 15 μm, followed by drying byheating at about 110° C. for about 5 minutes. Subsequently, MZ-100produced by Takamatsu Oil & Fat Co., Ltd. as an ink jet accepting agent(amorphous silicon dioxide, a mixture of polyurethane and vinyl resin,solid content of 15%, content of porous pigment in the solid content:about 56%) was applied to have a dried film thickness of about 30 μm,followed by drying by heating at about 110° C. for about 5 minutes. Onthe thus manufactured temporary displaying surface layer, an image wasprinted in a manner similar to Working Example 1. After that, a heattreatment was conducted for about 7 minutes using a hot-air drier (byYamato Scientific Co. Ltd., Fine Oven DF6L) set at about 170° C.,whereby the sublimable dye was allowed to sublimate and penetrate, sothat the image was printed in the colorable resin layer 2 in the side ofthe printing laminate. After that, the temporary displaying surfacelayer in a film state was peeled off.

Working Example 6

As the dye migration preventive layer 3 shown in FIG. 2, on ananneal-treated biaxially stretched polyester film (produced by TeijinDuPont Films Japan Limited, trade name MX534, shrinkage ratio at thetime of heating at 150° C. for 30 minutes is 0.3% in the windingdirection of the film, film thickness of 97 μm), the resin compositionfor the colorable resin layer 2, which was mixed similarly to WorkingExample 2, was applied to have a dried film thickness of about 20 μm,followed by drying by heating at about 140° C. for about 10 minutes,whereby the colorable resin layer 2 was manufactured.

Subsequently, on this colorable resin layer 2, the resin composition forthe surface resin layer 1 described in Working Example 2 was applied tohave a dried film thickness of about 20 μm, followed by drying byheating at about 140° C. for about 10 minutes, whereby the surface resinlayer 1 was obtained. On a rear face of the thus obtained biaxiallystretched polyester film that was the dye migration preventive layer ofthe printing laminate, an adhesive layer 5 and a releasing film 6 wasformed in a manner similar to Working Example 1 so as to form a finalproduct. Next, a printed surface of a transfer paper was applied to thesurface resin layer 1 in a manner similar to Working Example 1, so as toallow the image to be transferred into the colorable resin layer 2.

Comparative Example 1

The configuration, the dimensions, the manufacturing method and the likewere similar to those in Working Example 2 except that the step for thedye migration preventive layer 3 was omitted.

Comparative Example 2

The configuration, the dimensions, the manufacturing method and the likewere similar to those in Working Example 2 except that the steps for thedye migration preventive layer 3 and the flexible resin layer 4 wereomitted.

Comparative Example 3

The configuration, the dimensions, the manufacturing method and the likewere similar to those in Working Example 2 except that the mixtureliquid for the resin composition for the surface resin layer 1, thecolorable resin layer 2 and the dye migration preventive layer 3 werechanged as follows and the step for the flexible resin layer 4 wasomitted.

On a supporting film made of a biaxially stretched polyester film, toboth sides of which a treatment for facilitating the bonding had beenperformed (not annealed, used as the dye migration preventive layer 3),a polyurethane resin solution BURNOCK L7-920 (produced by Dainippon Inkand Chemicals, Inc., containing non-volatile matter of about 25±%,solvent: toluene, sec-butanol) was applied to have a dried filmthickness of about 20 μm, followed by drying by heating at about 140° C.for about 10 minutes, whereby the colorable resin layer 2 wasmanufactured. Subsequently, on this colorable resin layer 2, a vinylchloride resin coating having the following composition was applied tohave a dried film thickness of about 20 μm, followed by drying byheating at about 140° C. for 10 minutes, whereby the surface resin layer1 was formed:

(1) vinyl chloride resin 100 parts (2) ethylene/vinyl ester resin  25parts (3) polyester plasticizer  10 parts

Note here that NIKAVINYL SG-1100 N (produced by Nippon CarbideIndustries Co., Inc.) and Elvaloy (trade name, produced by DuPont-Mitsui Polychemical Co., Ltd.) respectively were used as the abovevinyl chloride resin and ethylene/vinylester resin. As the polyesterplasticizer, a material having a number-average molecular weight (Mn) ofabout 3,000 obtained by synthesizing mixed dihydric alcohol containingpropylene glycol, butanediol and hexanediol and adipic acid was used.

The following Tables 2 to 5 summarize the results of the estimationafter the image transferring and the examination methods of theabove-stated Examples and Comparative Examples.

TABLE 2 Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Property for keeping ◯ ◯ ◯ ◯ ◯ ◯sharpness of transferred image (A) ★ 1 Property for keeping ◯ ◯ ◯ ◯ ◯ ◯sharpness of transferred image (B) ★ 2 Property for keeping ◯ ◯ ◯ ◯ ◯ ◯sharpness of transferred image (C) ★ 3 Erichsen push out test ★ 4 Δ ◯ ◯◯ ◯ X State of wrinkles subjected to ◯ ◯ ◯ ◯ ◯ ◯ heat vacuum applicatortransferring ★ 5

TABLE 3 Comp. Ex 1 Comp. Ex 2 Comp. Ex 3 Property for keeping Δ Δ~X Xsharpness of transferred image (A) ★ 1 Property for keeping X X Xsharpness of transferred image (B) ★ 2 Property for keeping Δ Δ~X Xsharpness of transferred image (C) ★ 3 Erichsen push out test ★ 4 ◯ ◯ XState of wrinkles subjected ◯ ◯ X to heat vacuum applicator transferring★ 5

TABLE 4 Ex 6 Comp. Ex 3 cyan magenta yellow black cyan magenta yellowblack accelerated Before Y 8.32 10.13 65.97 0.74 8.83 10.81 68.61 0.74weather-proofness test x 0.1382 0.4845 0.4310 0.2346 0.1421 0.50130.4340 0.2481 test ★ 6 y 0.1409 0.2256 0.4953 0.2846 0.1347 0.23580.4924 0.2782 After test ΔE 3.45 4.81 5.19 2.90 19.35 11.34 16.06 11.57Appearance No abnormalities in image, fading Bleeding occurred aroundthe hardly was recognized, properties image, fading also was for keepinggloss also were remarkable. Scale of water was favorable. attached onthe sheet surface, thus degrading the gloss of the sheet surface.

TABLE 5 Ex 6 Comp. Ex 3 cyan magenta yellow black cyan magenta yellowblack outdoor weather Before Y 9.21 9.23 65.79 0.76 8.79 10.74 75.640.78 proofness test x 0.1352 0.5238 0.4316 0.2343 0.1383 0.5359 0.44100.2428 test ★ 7 y 0.1350 o.2429 0.4869 0.2508 0.1284 0.2526 0.48610.2717 After test ΔE 5.87 9.81 3.21 7.86 40.20 22.89 17.96 21.75Appearance No abnormalities in image, fading Bleeding occurredsignificantly hardly was recognized, properties around the image, theentire image for keeping gloss also were became blurred and fadingfavorable. occurred considerably. Stains were attached on the sheetsurface, thus darkening the sheet.(Remarks) The marks ★ 1 to 7 in Tables 2 to 5 are described below as(Remark 1) to (Remark 7).(Remark 1) 45° facing to the south, atmospheric exposure test (testinglocation: Wakayama prefecture, Japan), the testing time was one year. ◯(keeping the sharpness)>Δ (slightly bleeding in the image)>x (blurredimage and unclear)(Remark 2) UVCON (Atlas Material Testing Technology LLC, U.S.)accelerated weathering test

1 cycle: UV irradiation at 60° C. for 4 hours/condensation 40° C. for 4hours

testing time: 1,000 hours

◯ (keeping the sharpness)>Δ (slightly bleeding in the image)>x (blurredimage and unclear)

(Remark 3) Complying with conditions of the sunshine carbon typeaccelerated weathering test specified by JIS Z 9117. The testing timewas 1,000 hours

◯ (keeping the sharpness)>Δ (slightly bleeding in the image)>x (blurredimage and unclear)

(Remark 4) Erichsen tester (Toyo Seiki Seisaku-sho, LTD.)

Board for attachment: an aluminum plate with thickness of 1 mm and withharness of H24 of A50502P specified by JIS H 4000

Testing method: a printing laminate was attached to the board, which wasallowed to stand at room temperature for 48 hours. Subsequently, a punchwith radius of 10 mm was pushed against from the rear face of the board,and was pushed therein by 6 mm so as to form a curved surface.Thereafter, the UVCON accelerated weathering test in (Remark 2) wasconducted for 1,000 hours.

-   ◯: No abnormalities in the appearance;-   Δ: cracks occurred at the top of the extruded curved surface; and-   x: sheet as a whole swelled up from the board    (Remark 5) showing the state of a film subjected to the following    steps: thermo compression treatment was conducted using a heat    vacuum applicator (produced by HUNT EUROPE, VacuSeal 4468) at the    degree of vacuum of 3.99×10³ Pa (30 mmHg) and at the setting    temperature of about 170° C. for about 7 minutes. Thereby, heat was    applied to both of the printing laminate and the transfer paper so    as to allow the diffusion and the dyeing of the image printed in the    transfer paper to diffuse into the printing laminate, thus letting    the image to be transferred in the film.-   ◯: No abnormalities in the appearance; and-   x: Wrinkles occurred in the entire sheet.    (Remark 6) The testing method was the same as in (Remark 3).    Chrominance ΔE was measured by photoelectric tristimulus colorimetry    specified by JIS Z 8722 and was determined using the color    difference formula specified by “JIS Z 8730 chrominance presentation    method”.    (Remark 7) The testing method was the same as in (Remark 1).    Chrominance ΔE was measured similarly to (Remark 6).

As shown in the above Tables 2 to 5, since the flexible resin layer wasnot formed in Working Example 1, the suitability for the attachment on athree-dimensionally curved surface of this example was not good.However, the property for keeping the sharpness of the image wasexcellent and the state of the sheet after the heating for transfer alsowas favorable. Working Examples 2 to 5 were suitable for the attachmenton a three-dimensionally curved surface and had an excellent propertyfor keeping sharpness of the image. The state of the sheets of theseexamples after the heating for transfer also was favorable. As forWorking Example 6, the suitability for the attachment on athree-dimensionally curved surface of this example was not good.However, this example used an anneal-treated biaxially stretchedpolyester film as the dye migration preventive layer, and therefore theproperty for keeping the sharpness of image was excellent and nowrinkles were found in the sheet after the heating for transfer. Sincethe dye migration preventive layer 3 was not formed in ComparativeExamples 1 and 2, bleeding and the like occurred in the image and theproperty for keeping the sharpness of the image was poor. Since abiaxially stretched polyester film was used as the dye migrationpreventive layer of Comparative Example 3, the suitability for theattachment on a three-dimensionally curved surface of this example wasnot good, and wrinkles occurred in the sheet after the heating fortransfer. Furthermore, since a vinyl chloride resin was used as thesurface resin layer 1, the property for keeping the sharpness of theimage was poor, and the resistance to fading of the image also was poor.Thus, the printing laminate of the present invention, in which the dyemigration preventive layer 3 was formed, was free from the occurrence ofbleeding and blurs of the image even after it was allowed to stand for along time and could keep the sharpness of the image, so that theprinting laminate having excellent resistance to fading and weatherresistance could be realized. Furthermore, in the case where a biaxiallystretched polyester was used, the use of an anneal-treated film couldprevent the occurrence of wrinkles due to heating. Moreover, by formingthe flexible resin layer 4 under the dye migration preventive layer 3,this printing laminate can be applied successfully to the attachment ona curved surface.

INDUSTRIAL APPLICABILITY

According to the present invention, a dye migration preventive colorableresin layer having affinity with a sublimable dye and preventing themigration of the dye is formed as an internal layer. Thereby, a printinglaminate that can prevent the migration of the printed sublimable dye,and a printing method and a print using the same can be provided.Furthermore, according to the present invention, a flexible layer havingan elongation percentage larger than that of the dye migrationpreventive colorable resin layer further is provided below the dyemigration preventive colorable resin layer. Thereby, a printing laminatehaving flexibility that enables the attachment on a curved surface of asubstrate, and a printing method and a print using the same can beprovided.

1. A printing laminate in which a sublimable dye is allowed to penetratea resin layer by application of heat so as to color the resin layer,comprising: a surface resin layer (A) that has weak affinity with asublimable dye and that has a permeability of the dye; a colorable resinlayer (B1) that has affinity with the dye, laminated below the surfaceresin layer (A); and a dye migration preventive layer (B2) that preventsmigration of the dye, laminated below the colorable resin layer (B1),wherein the dye migration preventive layer (B2) is a resin containing asa main component a vinyl resin having a glass transition temperature(Tg) of 70° C. or more and a SP value (Solubility Parameter) of 9.0 ormore, a thickness of the dye migration preventive layer (B2) being from1 μm to 100 μm, and the resin being cross-linked with a hardeningsubstance.
 2. The printing laminate according to claim 1, furthercomprising a flexible resin layer (C) that has an elongation percentagelarger than that of the dye migration preventive layer (B2), theflexible resin layer (C) being provided at a further lower layer thanthe dye migration preventive layer (B2).
 3. The printing laminateaccording to claim 2, further comprising a layer including highrefractive glass beads laminated below the flexible resin layer, and ametal reflective layer coated and formed below the layer including thehigh refractive glass beads, so as to provide a retroreflective layer.4. The printing laminate according to claim 2, further comprising alayer in which high refractive glass beads are fixed and a focus resinlayer, laminated successively below the flexible resin layer (C), and ametal reflective layer further coated and formed below the focus resinlayer, so as to provide a retroreflective layer.
 5. The printinglaminate according to claim 2, wherein, in a retroreflective sheetcomprising: a plurality of transparent beads whose lower hemispheres areeach provided with a metal reflective layer; a supporting resin sheetsupporting the plurality of transparent beads; and a transparent coverfilm covering the plurality of transparent beads by being disposed on asurface side of the supporting resin sheet, wherein a bonding portionfor holding the cover film is provided in the supporting resin sheet,the cover film is the printing laminate.
 6. The printing laminateaccording to claim 1, wherein the dye migration preventive layer (B2) isa layer comprising a three dimensional polymer in which a resincontaining as a main component a vinyl resin having a glass transitiontemperature (Tg) of 70° C. or more and a SP value (Solubility Parameter)of 9.0 or more is cross-linked with a hardening substance.
 7. A printinglaminate in which a sublimable dye is allowed to penetrate a resin layerby application of heat so as to color the resin layer, comprising: asurface resin layer (A) that has weak affinity with the sublimable dyeand that has a permeability of the dye; a colorable resin layer (B1)that has affinity with the dye, laminated below the surface resin layer(A); and a dye migration preventive layer (B2) that prevents migrationof the dye, laminated below the colorable resin layer wherein the dyemigration preventive layer (B2) is a biaxially stretched film that isstretched by 10% or more in a winding direction and in a width directionand that has a shrinkage ratio of 1.0% or less in the winding directionof the film at the time of heating at 150° C. for 30 minutes.
 8. Theprinting laminate according to claim 1 or 7, wherein the surface resinlayer (A) is formed of a fluororesin comprising a fluoroolefin copolymerthat is soluble in a solvent.
 9. The printing laminate according toclaim 1 or 7, wherein the surface resin layer (A) is formed of a silicondenatured acrylic resin.
 10. The printing laminate according to claim 1or 7, wherein the colorable resin layer (B1) is a resin containing about20 weight % or less of a low molecular-weight compound having amolecular weight of about 1,300 or less.
 11. The printing laminateaccording to claim 1 or 7, wherein a matting agent is added to thesurface resin layer (A) so as to decrease a 60° gloss of the surfacelayer to 70 or less.
 12. The printing laminate according to claim 1 or7, wherein at least one layer of the surface resin layer (A) and thecolorable resin layer (B1) contains at least one type selected from thegroup consisting of a high molecular-weight type ultraviolet absorber, ahigh molecular-weight type hindered amine light stabilizer, and a highmolecular-weight type hindered phenol antioxidant.
 13. The printinglaminate according to claim 1 or 7, wherein light diffusing fineparticles are added to at least one layer of the surface resin layer(A), the dye migration preventive layer (B2) and each layer below theselayers, so as to assign a light diffusing property to these layers. 14.The printing laminate according to claim 1 or 7, wherein a white pigmentis used for at least one layer of the colorable resin layer (B1) and thedye migration preventive layer (B2) so as to form a white Layer, thusenhancing a transmittance density of a printed image.
 15. The printinglaminate according to claim 1 or 7, further comprising a layer includinghigh refractive glass beads laminated below the dye migration preventivelayer (B2), and a metal reflective layer coated and formed below thelayer including the high refractive glass beads, so as to provide aretroreflective layer.
 16. The printing laminate according to claim 1 or7, further comprising a layer in which high refractive glass beads arefixed and a focus resin layer, laminated successively below the dyemigration preventive layer (B2), and a metal reflective layer furthercoated and formed below the focus resin layer, so as to provide aretroreflective layer.
 17. The printing laminate according to claim 1 or7, wherein, in a retroreflective sheet comprising: a plurality oftransparent beads whose lower hemispheres are each provided with a metalreflective layer; a supporting resin sheet supporting the plurality oftransparent beads; and a transparent cover film covering the pluralityof transparent beads by being disposed on a surface side of thesupporting resin sheet, wherein a bonding portion for holding the coverfilm is provided in the supporting resin sheet, the cover film is theprinting laminate.
 18. The printing laminate according to claim 1 or 7,wherein the surface resin layer (A) is coated with a coating formationcomposition including fine particles made of hydrotalcites and metaloxide, the hydrotalcites being represented by [M²⁺ _(1-X)M³⁺_(X)(OH)₂]^(X+)[A^(n−) _(X/n).mH₂O]^(X−), wherein M²⁺ denotes divalentmetal ions, M³⁺ denotes trivalent metal ions, A^(n−) denotes anions,0<X≦0.33, 0≦m≦2.
 19. The printing laminate according to claim 1 or 7,wherein on a rear face of the printing laminate, an adhesive layerfurther is provided and a releasing member further is provided on anoutside of the adhesive layer, and an antistatic treatment is applied tothe adhesive layer or the releasing member.
 20. The printing laminateaccording to claim 1 or 7, wherein at least one layer of a peelabletemporary displaying layer for enabling printing and displaying furtheris provided on the surface resin layer (A), and a face of the temporarydisplaying layer on a side that does not contact with the surface resinlayer (A) is capable of absorbing an ink containing a sublimable dye andis capable of allowing the sublimable dye to sublimate by application ofheat so as to allow diffusion and dyeing in the printing laminate, andafter heating, the temporary displaying layer is capable of being peeledoff from the surface resin layer (A) of the printing laminate whilekeeping a film state.
 21. A printing method using the printing laminateaccording to claim 20, wherein printing is conducted with respect to thetemporary displaying layer of the printing laminate using an inkcontaining a sublimable dye.
 22. A printing method using the printinglaminate according to claim 20, wherein printing is conducted withrespect to the temporary displaying layer of the printing laminate usingan ink containing a sublimable dye, and subjecting a heat treatment soas to sublimate the sublimable dye, thus allowing diffusion of thesublimable dye into the colorable resin layer (B1) to dye the same. 23.A printing method by which printing is conducted with respect to aprinting laminate in which a sublimable dye is allowed to penetrate aresin layer by application of heat so as to color the resin layer, theprinting laminate comprising, a surface resin layer (A) that has weakaffinity with the sublimable dye and that has a permeability of the dye;a colorable resin layer (B1) that has affinity with the dye and a dyemigration preventive layer (B2) that prevents migration of the dye,which are laminated in this stated order from a surface of the laminate,wherein the dye migration preventive layer (B2) is a resin containing asa main component a vinyl resin having a glass transition temperature(Tg) of 70° C. or more and a SP value of 9.0 or more, a thickness of thedye migration preventive layer (B2) being from 1 μm to 100 μm, and theresin being cross-linked with a hardening substance, the printing methodcomprising the steps of: conducting printing with respect to a transferpaper using an ink containing a sublimable dye; and bringing an imageformation face of the transfer paper in contact with the surface resinlayer (A), followed by a heat treatment so as to sublimate thesublimable dye, thus allowing diffusion of the sublimable dye into thecolorable resin layer (B1) to dye the same.
 24. The printing methodaccording to claim 23, wherein the printing is conducted by an ink jetmethod.
 25. The printing method according to claim 23, wherein atemperature of the heat treatment is within a range from 150 to 200° C.26. The printing method according to claim 23, further comprising a stepof drying the printed ink, conducted between the printing and the heattreatment.
 27. A print with respect to which printing is conducted usinga printing laminate in which a sublimable dye is allowed to penetrate aresin layer by application of heat so as to color the resin layer, theprinting laminate comprising, a surface resin layer (A) that has weakaffinity with the sublimable dye and that has a permeability of the dye;a colorable resin layer (B1) that has affinity with the dye and a dyemigration preventive layer (B2) that prevents migration of the dye,which are laminated in this stated order from a surface of the laminate,wherein the dye migration preventive layer (B2) is a resin containing asa main component a vinyl resin having a glass transition temperature(Tg) of 70° C. or more and a SP value of 9.0 or more, a thickness of thedye migration preventive layer (B2) being from 1 μm to 100 μm, and theresin being cross-linked with a hardening substance, wherein theprinting is conducted with respect to a transfer paper using an inkcontaining a sublimable dye; and an image formation face of the transferpaper is brought in contact with the surface resin layer (A), followedby a heat treatment so as to sublimate the sublimable dye, thus allowingdiffusion of the sublimable dye into the colorable resin layer (B1) todye the same.